JP6882000B2 - Method for manufacturing crosslinked molded article - Google Patents

Description

The present invention relates to a method for producing a crosslinked molded product composed of an ethylene / α-olefin / non-conjugated polyene copolymer composition by an injection molding method.

A copolymer composition (Patent Document 1) obtained by hydrosilyl cross-linking of an ethylene / α-olefin / non-conjugated polyene random copolymer (hereinafter, may be abbreviated as EPDM) is obtained by sulfur vulcanization or peroxide cross-linking. Compared to the above, it has excellent mechanical strength, heat aging resistance, compression set, and bloom property, and is capable of continuous cross-linking. It is expected to be applied to sealing parts such as packings and gaskets.

On the other hand, as one of the methods for obtaining a molded product from a rubber composition, a method using an injection molding machine (injection molding machine) has been proposed, but since the rubber composition needs to be crosslinked at a high temperature, injection is performed. The molding time (one cycle) is extremely long compared to the time required to obtain a molded product such as polyethylene or polypropylene that is easily cooled and solidified in the molding mold.

For example, even if the rubber composition described in Patent Document 1 is used, the rubber composition has a short scorch time and a slow cross-linking speed. Therefore, even if an injection molding machine is used to obtain a cross-linked molded product, injection molding is performed. Cross-linking starts in the machine and the processability of extrusion-injection molding deteriorates, and in order to cross-link, it is necessary to hold the molded product in the mold for a relatively long time, in any case. , There was a problem in obtaining a crosslinked molded product by injection molding.

Japanese Unexamined Patent Publication No. 2006-290917

The present invention is to develop a composition capable of shortening one cycle in injection molding.

The present invention describes the ethylene / α-olefin / non-conjugated polyene copolymer described in the present application, which has a low long-chain branching content and is excellent in curing characteristics when cross-linking, and is excellent in controlling the cross-linking behavior. It has been found that the above problems can be solved by combining with a cross-linking agent.

That is, the present invention comprises an ethylene / α-olefin / non-conjugated polyene copolymer (S), a hydrosilyl group-containing compound (Y) having at least two hydrosilyl groups in one molecule, and a platinum-based compound for hydrosilicon crosslinking. the catalyst (Z), and a reaction inhibitor, a composition comprising melt-kneaded, injection molded into the mold, according to the method for producing a molded article characterized by crosslinking in the die ..

According to the present invention, it is possible to shorten the molding time (one cycle) of injection molding of a crosslinked molded product composed of an ethylene / α-olefin / non-conjugated polyene copolymer, and to obtain a molded product having an excellent surface appearance and the like. Can be provided.

<Ethylene / α-olefin / non-conjugated polyene copolymer (S)>
The ethylene / α-olefin / non-conjugated polyene copolymer (S) contained in the ethylene / α-olefin / non-conjugated polyene copolymer composition used in the method for producing the molded product of the present invention contains ethylene (A). , An unconjugated polyene (C) containing two or more α-olefins (B) having 3 to 20 carbon atoms and a partial structure selected from the group consisting of the following general formulas (I) and (II) in a total molecule. It has a constituent unit derived from.

このような本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）は、上記（Ａ）、（Ｂ）、（Ｃ）に由来する構造単位に加えて、さらに上記一般式（Ｉ）および（II）からなる群から選ばれる部分構造を分子中に１つのみ含む非共役ポリエン（Ｄ）に由来する構成単位を有していてもよい。

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention has the above general formula (S) in addition to the structural units derived from the above (A), (B) and (C). It may have a structural unit derived from a non-conjugated polyene (D) containing only one partial structure selected from the group consisting of I) and (II) in the molecule.

Examples of the α-olefin (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-. Examples thereof include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferable, and propylene is particularly preferable. Such an α-olefin has a relatively low raw material cost, the obtained ethylene / α-olefin / non-conjugated polyene copolymer exhibits excellent mechanical properties, and a molded product having rubber elasticity is obtained. It is preferable because it can be used. These α-olefins may be used alone or in combination of two or more.

That is, the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention contains at least one structural unit derived from the α-olefin (B) having 3 to 20 carbon atoms. It may contain a structural unit derived from two or more kinds of α-olefins (B) having 3 to 20 carbon atoms.

Examples of the non-conjugated polyene (C) containing two or more partial structures selected from the group consisting of the general formulas (I) and (II) in the molecule include 5-vinyl-2-norbornene (VNB), norbornadiene, and the like. Examples thereof include 1,4-hexadiene and dicyclopentadiene. Among these, the non-conjugated polyene (C) preferably contains VNB because it is easily available, has good hydrosilyl cross-linking, and easily improves the heat resistance of the polymer composition, and the non-conjugated polyene (C) is preferably contained. Is more preferably VNB. The non-conjugated polyene (C) may be used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention is derived from ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, and the non-conjugated polyene (C). In addition to the structural unit, it may further contain a structural unit derived from a non-conjugated polyene (D) containing only one partial structure selected from the group consisting of the general formulas (I) and (II) in the molecule. Good. Examples of such non-conjugated polyene (D) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (3-butenyl). -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5 -(5-Hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-) Ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4- Pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene , 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-Norbornene and the like. Among these, ENB is preferable because it is easily available, the cross-linking rate at the time of hydrosilyl cross-linking is easily controlled, and good mechanical properties can be easily obtained. The non-conjugated polyene (D) may be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is a non-conjugated polyene (D) containing only one partial structure selected from the group consisting of the general formulas (I) and (II) in the molecule. When the derived structural unit is included, the proportion thereof is not particularly limited as long as the object of the present invention is not impaired, but is usually 0 to 20% by weight, preferably 0 to 8% by weight, and more preferably 0. It is included in a weight fraction of about 01 to 8% by weight (however, the total weight fraction of (A), (B), (C), and (D) is 100% by weight).

As described above, the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention contains ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and the above-mentioned non-conjugated polyene. A copolymer having a structural unit derived from (C) and, if necessary, the non-conjugated polyene (D), which satisfies the following requirements (i) to (v).
(I) The molar ratio of ethylene / α-olefin is 40/60 to 99.9 / 0.1.
(Ii) The weight fraction of the structural unit derived from the non-conjugated polyene (C) is 0.07% by weight to 10% by weight.
(Iii) The weight average molecular weight (Mw) of the ethylene / α-olefin / non-conjugated polyene copolymer and the weight fraction (% by weight) of the structural unit derived from the non-conjugated polyene (C). )) And the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)) satisfy the following formula (1).
4.5 ≤ Mw x (C) weight fraction / 100 / (C) molecular weight ≤ 40 ... Equation (1)
^{(Iv) Complex viscosity η *} ₍ ω _{= 0.1)} (Pa · sec) at frequency ω = 0.1 rad / s and frequency ω = obtained by linear viscous elasticity measurement (190 ° C.) using a leometer. ^{The ratio P (η *} ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ^{) to the complex viscosity η *} ₍ ω _{= 100)} (Pa · sec) at 100 rad / s, the ultimate viscosity [η], and the above. The weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≤ (C) x 6 ... Equation (2)
(V) The number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained by using 3D-GPC and the natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) are expressed by the following formula (3). Meet.
LCB _1000C ≤1-0.07 × Ln (Mw) ‥ Equation (3)

In the present specification, the above (i) to (v) are also referred to as requirements (i) to (v), respectively. Further, in the present specification, "α-olefin having 3 to 20 carbon atoms" is also simply referred to as "α-olefin".

<Requirement (i)>
The requirement (i) is that the molar ratio of ethylene / α-olefin in the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention satisfies 40/60 to 99.9 / 0.1. The molar ratio is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and even more preferably 55/45 to 78/22. Such an ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is preferable because the molded product obtained by hydrosilyl cross-linking exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility. ..

The amount of ethylene in the ethylene / α-olefin / non-conjugated polyene copolymer (S) (content of the structural unit derived from ethylene (A)) and the amount of α-olefin (structure derived from α-olefin (B)). The unit content) can be determined by ^{13 C-NMR.}

<Requirements (ii)>
The requirement (ii) is that in the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention, the weight fraction of the structural unit derived from the non-conjugated polyene (C) is ethylene / α-olefin. It specifies that the non-conjugated polyene copolymer (S) is in the range of 0.07% by weight to 10% by weight in 100% by weight (that is, in 100% by weight of the total weight fraction of all constituent units). is there. The weight fraction of the structural unit derived from this non-conjugated polyene (C) is preferably 0.1% by weight to 8.0% by weight, more preferably 0.5% by weight to 5.0% by weight. desirable.

When the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention satisfies the requirement (ii), the ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention is sufficient. It is preferable because it has hardness and excellent mechanical properties, and when it is hydrosilyl crosslinked, it exhibits a high crosslink rate, and the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention. However, it is preferable because it is suitable for producing a crosslinked molded product.

The amount of non-conjugated polyene (C) in the ethylene / α-olefin / non-conjugated polyene copolymer (S) (content of structural units derived from non-conjugated polyene (C)) shall ^{be determined by 13} C-NMR. Can be done.

<Requirement (iii)>
Requirement (iii) is the weight average molecular weight (Mw) and the common weight of the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention. The weight fraction of the constituent unit derived from the non-conjugated polyene (C) in the coalescence (weight fraction of (C):% by weight) and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) are It specifies that the following relational expression (1) is satisfied.
4.5 ≤ Mw x (C) weight fraction / 100 / (C) molecular weight ≤ 40 ... Equation (1)

When the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention satisfies the requirement (iii), the content of the structural unit derived from the non-conjugated polyene (C) such as VNB is appropriate. When a crosslinked molded product is produced using the ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention, the crosslinking rate is excellent and the crosslinked product is excellent. It is preferable because the molded product exhibits excellent mechanical properties.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention more preferably satisfies the following relational expression (1').
4.5 ≤Mw x (C) weight fraction / 100 / (C) molecular weight ≤35 ... Equation (1')
The weight average molecular weight (Mw) of the ethylene / α-olefin / non-conjugated polyene copolymer (S) can be determined as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

In the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention, the "weight fraction of Mw × (C) / molecular weight of 100 / (C)" is the above formula (1) or (1'). ) Is satisfied, the degree of cross-linking becomes appropriate, and by using this, a molded product having an excellent balance between mechanical properties and heat aging resistance can be produced. If the "weight fraction of Mw x (C) / 100 / molecular weight of (C)" is too small, the cross-linking property may be insufficient and the cross-linking rate may be slowed down during hydrosilyl cross-linking. If it is too much, excessive cross-linking may occur and the mechanical properties may deteriorate.

<Requirements (iv)>
Requirement (iv) is the frequency ω = 0. Obtained by linear viscous elasticity measurement (190 ° C.) of the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention using a leometer. ^{The ratio P (η *} ) of the complex viscosity η ^* ₍ ω _{= 0.1)} (Pa · sec) at 1 rad / s to the complex viscosity η ^* ₍ ω _{= 100)} (Pa · sec) at the frequency ω = 100 rad / s. ₍ Ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ), the ultimate viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C): weight% ) Satisfies the following equation (2).
Weight fraction of P / ([η] ^2.9 ) ≤ (C) x 6 ... Equation (2)

Here, the ratio P (η ^* ₍ ω)) of the complex viscosity η ^* ₍ ω _{= 0.1)} ^{at the frequency ω = 0.1 rad / s to the complex viscosity η *} ₍ ω _{= 100)} at the frequency ω = 100 rad / s. _{= 0.1)} / η ^* ₍ ω _{= 100)} ) represents the frequency dependence of viscosity, and P / ([η] ^2.9 ), which corresponds to the left side of equation (2), indicates short-chain branching, molecular weight, etc. Although there is an effect, it tends to show a high value when there are many long-chain branches. Generally, in an ethylene / α-olefin / non-conjugated polyene copolymer, the more structural units derived from the non-conjugated polyene, the more long-chain branches tend to be contained. It is considered that the non-conjugated polyene copolymer (S) can satisfy the above formula (2) because it has fewer long-chain branches than the conventionally known ethylene / α-olefin / non-conjugated polyene copolymer. In the present invention, the P value is a complex viscosity at 0.1 rad / s obtained by measuring with a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under the conditions of 190 ° C., strain 1.0%, and frequency change. And the complex viscosity at 100 rad / s, the ratio (η * ratio) was calculated.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention preferably satisfies the following formula (2').
Weight fraction of P / ([η] ^2.9 ) ≤ (C) x 5.7 ... Equation (2')
The ultimate viscosity [η] means a value measured in decalin at 135 ° C.

<Requirement (v)>
_{The requirement (v) is the number of long-chain branches (LCB 1000C} ) per 1000 carbon atoms obtained by using 3D-GPC of the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention. , The natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) satisfies the following formula (3).
LCB _1000C ≤1-0.07 × Ln (Mw) ‥ Equation (3)

From the above formula (3), the upper limit of the long chain branching content per unit carbon number of the ethylene / α-olefin / non-conjugated polyene copolymer (S) is specified.
Such an ethylene / α-olefin / non-conjugated polyene copolymer (S) contains a small proportion of long-chain branches, is excellent in curing characteristics when hydrosilyl cross-linking is performed, and is a molded product obtained by using the copolymer. Is preferable because it has excellent heat aging resistance.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention preferably satisfies the following formula (3').
LCB _1000C ≤ 1-0.071 × Ln (Mw) ‥ Equation (3')
Here, Mw and the number of long-chain branches per 1000 carbon atoms (LCB _1000C ) can be obtained by a structural analysis method using 3D-GPC. Specifically, in the present specification, it is obtained as follows.

Using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), the absolute molecular weight distribution was determined, and at the same time, the ultimate viscosity was determined with a viscometer. The main measurement conditions are as follows.
Detector: Built-in differential refractometer / GPC device
2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors)
Bridge type viscometer PL-BV400 type (manufactured by Polymer Laboratories)
Column: TSKgel GMH _HR -H (S) HT x 2 + TSKgel GMH _HR -M (S) x 1
(In each case, inner diameter 7.8 mmφ x length 300 mm)
Temperature: 140 ℃
Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT)
Injection volume: 0.5 mL
Sample concentration: ca 1.5 mg / mL
Sample filtration: Filtration with a 1.0 μm sintered filter The dn / dc value required to determine the absolute molecular weight is based on the dn / dc value of 0.053 for standard polystyrene (molecular weight 190000) and the response strength of the differential refractometer per unit injection mass. , Determined for each sample.

The long-chain branching parameter g'i for each elution component was calculated from the equation (v-1) from the relationship between the ultimate viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer.

ここで、［η］=ＫＭ^v；ｖ＝0.725の関係式を適用した。
また、ｇ'として各平均値を下記式（ｖ−２）、（ｖ−３）、（ｖ−４）から算出した。なお、短鎖分岐のみを有すると仮定したTrendlineは試料ごとに決定した。

Here, the relational expression of [η] = KM ^v ; v = 0.725 was applied.
Further, each average value was calculated as g'from the following formulas (v-2), (v-3), and (v-4). The Trendline, which was assumed to have only short-chain branches, was determined for each sample.

更にｇ'wを用いて、分子鎖あたりの分岐点数ＢrＮo、炭素１０００個あたりの長鎖分岐数ＬＣＢ_1000C、単位分子量あたりの分岐度λを算出した。ＢrＮo算出はZimm-Stockmayerの式（ｖ−５）、また、ＬＣＢ_1000Cとλの算出は式（ｖ−６）、（ｖ−７）を用いた。ｇは慣性半径Rgから求められる長鎖分岐パラメーターであり、極限粘度から求められるｇ'との間に次の単純な相関付けが行われている。式中のεは分子の形に応じて種々の値が提案されている。ここではε＝１（すなわちｇ'＝ｇ）と仮定して計算を行った。

Further, using g'w, the number of branch points BrNo per molecular chain, the number of long chain branching LCB _1000C per 1000 carbons, and the degree of branching λ per unit molecular weight were calculated. The BrNo calculation used the Zimm-Stockmayer equation (v-5), and the LCB _1000C and λ were calculated using the equations (v-6) and (v-7). g is a long-chain branching parameter obtained from the radius of inertia Rg, and the following simple correlation is made with g'determined from the ultimate viscosity. Various values of ε in the formula have been proposed depending on the shape of the molecule. Here, the calculation was performed on the assumption that ε = 1 (that is, g'= g).

λ＝ＢｒＮｏ／Ｍ …（Ｖ−６）
ＬＣＢ_1000C＝λ×１４０００ …（Ｖ−７）
＊式（Ｖ−７）中、１４０００はメチレン（ＣＨ²）単位で１０００個分の分子量を表す。

λ = BrNo / M ... (V-6)
LCB _1000C = λ × 14000… (V-7)
* In the formula (V-7), 14000 represents the molecular weight of 1000 pieces in ^{methylene (CH 2) units.}

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention preferably has an intrinsic viscosity [η] of 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g. More preferably, it is 0.9 to 4.0 dL / g.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 600,000, more preferably 30,000 to 500,000. More preferably, it is 50,000 to 400,000.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention is preferably satisfied with the above-mentioned ultimate viscosity [η] and weight average molecular weight (Mw).
In the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention, the non-conjugated polyene (C) preferably contains VNB, and more preferably VNB. That is, in the above formulas (1) and (2) and the formula (4) described later, it is preferable that the "weight fraction of (C)" is the "weight fraction of VNB" (% by weight).

As described above, the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention further comprises the structural units derived from the above (A), (B) and (C). A structural unit derived from a non-conjugated polyene (D) containing only one partial structure selected from the group consisting of the general formulas (I) and (II) in a molecule, and a weight fraction of 0% by weight to 20% by weight ( However, it is also preferable to include (A), (B), (C), and (D) in (the total weight fraction is 100% by weight). In this case, it is preferable to satisfy the requirement (vi) below.

(Requirements (vi))
The weight average molecular weight (Mw) of the ethylene / α-olefin / non-conjugated polyene copolymer (S) and the weight fraction (% by weight) of the structural unit derived from the non-conjugated polyene (C). )), The weight fraction of the constituent unit derived from the conjugated polyene (D) (the weight fraction (% by weight) of (D)), the molecular weight of the non-conjugated polyene (C) (the molecular weight of (C)), The molecular weight of the conjugated polyene (D) (the molecular weight of (D)) satisfies the following formula (4).

4.5 ≤ Mw x {((C) weight fraction / 100 / (C) molecular weight) + ((D) weight fraction / 100 / (D) molecular weight)} ≤ 45 ... Equation (4)
In the formula (4), the content of the unconjugated diene (the sum of (C) and (D)) in one molecule of the copolymer is specified.

When the ethylene / α-olefin / non-conjugated polyene copolymer (S) containing the structural unit derived from the above (D) satisfies the formula (4), the ethylene / α-olefin / non-conjugated polyene copolymer (S) The hydroxycrosslinked molded product obtained from the above composition is preferable because it exhibits excellent mechanical properties and heat aging resistance.

The requirement (vi) is not satisfied, and “Mw × {(weight fraction of (C) / 100 / molecular weight of (C)) + (weight fraction of (D) / 100 / (D)) in the formula (4). If the molecular weight of)} ”is too small, that is, if the content of non-conjugated diene is too small, sufficient cross-linking may not be performed and appropriate mechanical properties may not be obtained, and if it is too large, hydroxy cross-linking may be excessive. In addition to the deterioration of mechanical properties, the heat-resistant aging property may deteriorate.

<Requirements (vii)>
The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention is not particularly limited, but has a frequency ω obtained by linear viscoelasticity measurement (190 ° C.) using a leometer. Non-conjugated with complex viscosity η ^* ₍ ω _{= 0.01)} ^{(Pa · sec) at = 0.01 rad / s and complex viscosity η *} ₍ ω _{= 10)} (Pa · sec) at frequency ω = 10 rad / s. It is preferable that the apparent iodine value derived from the polyene (c) satisfies the following formula (5).

Log {η ^* ₍ ω _{= 0.01)} } / Log {η ^* ₍ ω _{= 10)} } ≤0.0753 × {apparent iodine value derived from non-conjugated polyene (C)} +1.42… Equation (5)
Here, the complex viscosity η ^* ₍ ω _{= 0.01)} and the complex viscosity η ^* ₍ ω _{= 10)} are measured as the ^{complex viscosity η *} ₍ ω _{= 0.1)} and the complex viscosity η ^* ₍ ω _{= 100)} in the requirement (vi). Other than the frequency, it is obtained in the same way.

The apparent iodine value derived from the non-conjugated polyene (C) is calculated by the following formula.
Apparent iodine value derived from (C) = weight fraction of (C) × molecular weight of 253.81 / (C) In the above formula (5), the left side represents the shear rate dependence which is an index of the long chain branching amount. The right side represents an index of the content of non-conjugated polyene (C) that is not consumed as a long-chain branch during polymerization. When the requirement (vii) is satisfied and the above equation (5) is satisfied, the degree of long chain branching is not too high, which is preferable. On the other hand, when the above formula (5) is not satisfied, it can be seen that the proportion of the copolymerized non-conjugated polyene (C) consumed for the formation of the long chain branch is large.

Further, the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention preferably contains a sufficient amount of a structural unit derived from the non-conjugated polyene (C), and is non-conjugated in the copolymer. The weight fraction of the constituent unit derived from the polyene (C) (weight fraction (% by weight) of (C)) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6). preferable.
6-0.45 x Ln (Mw) ≤ (C) weight fraction ≤ 10 ... Equation (6)

Further, in the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention, the number of structural units (n _C ) derived from the non-conjugated polyene (C) per weight average molecular weight (Mw) is large. It is preferably 6 or more, more preferably 6 or more and 40 or less, still more preferably 7 or more and 39 or less, and even more preferably 10 or more and 38 or less.

Such an ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention contains a sufficient amount of a structural unit derived from the non-conjugated polyene (C) such as VNB, and contains a long-chain branch. It has a small amount, is excellent in curing properties when cross-linking is performed using a peroxide, has good moldability, has an excellent balance of physical properties such as mechanical properties, and is particularly excellent in heat aging resistance.

Further, the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention has a number of structural units (n _D ) derived from the non-conjugated polyene (D) per weight average molecular weight (Mw). It is preferably 29 or less, more preferably 10 or less, and even more preferably less than 1.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention has a range in which the content of the structural unit derived from the non-conjugated polyene (D) such as ENB does not impair the object of the present invention. It is preferable because it is suppressed to polyene, less likely to cause post-crosslinking, and has sufficient heat aging resistance.

_{Here, the number of structural units (n C} ) derived from the non-conjugated polyene (C) or the non-conjugated polyene (n C) per weight average molecular weight (Mw) of the ethylene / α-olefin / non-conjugated polyene copolymer (S). _{The number of structural units (n D} ) derived from C) is the molecular weight of the non-conjugated polyene (C) or (D) and the number of structural units derived from the non-conjugated polyene (C) or (D) in the copolymer. It can be calculated by the following formula from the weight fraction (weight fraction (% by weight) of (C) or (D)) and the weight average molecular weight (Mw) of the copolymer.
(N _C ) = (Mw) × {weight fraction of (C) / 100} / molecular weight of non-conjugated polyene (C) (n _D ) = (Mw) × {weight fraction of (D) / 100} / Molecular weight of non-conjugated polyene (D)

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention has the number of structural units derived from the non-conjugated polyenes (C) and (D) per weight average molecular weight (Mw) ( When both n _c ) and (n _D ) satisfy the above range, the ethylene / α-olefin / non-conjugated polyene copolymer (S) has a small long-chain branching content and ethylene. When a composition containing an α-olefin / non-conjugated polyene copolymer (S) is hydroxy-crosslinked, the cross-linking rate is high, the resulting cross-linked molded product has an excellent balance of physical properties such as mechanical properties, and post-cross-linking occurs. It is preferable because it is difficult and particularly excellent in heat aging resistance.

<Production of ethylene / α-olefin / non-conjugated polyene copolymer (S)>
The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention includes ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, and the general formulas (I) and (I). A non-conjugated polyene (C) containing two or more partial structures selected from the group consisting of II) in total, and a partial structure selected from the groups consisting of the general formulas (I) and (II) as necessary. It is a copolymer obtained by copolymerizing a monomer composed of a non-conjugated polyene (D) containing only one and two in the molecule in total.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention may be prepared by any production method as long as the above requirements (i) to (v) are satisfied, but is a metallocene compound. It is preferably obtained by copolymerizing a monomer in the presence of a metallocene compound, and more preferably obtained by copolymerizing a monomer in the presence of a catalytic system containing a metallocene compound.

The ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention is specifically produced, for example, by adopting the method described in the metallocene catalyst described in International Publication No. 2015/122495. can do.

<Hydrosilyl group-containing compound (Y)>
The hydrosilyl group-containing compound (Y) according to the present invention reacts with an ethylene / α-olefin / non-conjugated polyene copolymer (S) and acts as a cross-linking agent. This hydrosilyl group-containing compound (Y) can be used in any of the conventionally manufactured and commercially available structures, for example, a linear, cyclic, branched structure, or a resin-like substance having a three-dimensional network structure. However, the hydrosilyl group-containing compound (Y) used in the present invention must contain at least two hydrosilyl groups in one molecule.

Such a hydrosilyl group-containing compound (Y) is usually prepared by the following general composition formula R ⁴ _b H _c SiO _{(4-bc) / 2.}
The compound represented by is used.

In the above general composition formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding the aliphatic unsaturated bond, and such 1 The valent hydrocarbon group includes an alkyl group containing isomers such as n-, iso-, sec-, and tert-, starting from a methyl group and an ethyl group, and reaching a nonyl group and a decyl group, a phenyl group, and a halogen-substituted alkyl group. For example, a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group is particularly preferable.

In the above general composition formula, b is 1 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 1 <c ≦ 3, preferably. Is 1 ≦ c <2, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.

The hydrosilyl group-containing compound (Y) according to the present invention is an organohydrogenpolysiloxane in which the number of silicon atoms in one molecule is preferably 2 to 1000, particularly preferably 2 to 300, and most preferably 4 to 200. Yes, specifically, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane, etc. Siloxane oligomer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, silanol group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, molecular chain Both-terminal dimethylhydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, consisting of R ² ₂ (H) SiO _1/2 unit and SiO _4/2 unit, optionally R ² ₃ SiO _1/2 unit , R ² ₂ SiO _2/2 units, R ² (H) SiO _2/2 units, (H) SiO _3/2 or R ² SiO _3/2 units, silicone resins and the like.

Examples of the methylhydrogenpolysiloxane that blocks the trimethylsiloxy group at both ends of the molecular chain include a compound represented by the following formula, and a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, or a trifluoropropyl group. Examples thereof include compounds substituted with or the like.
(CH ₃ ) ₃ SiO-(-SiH (CH ₃ ) -O-) _d- Si (CH ₃ ) ₃
(D in the formula is an integer of 2 or more.)

As the dimethylsiloxane / methylhydrogensiloxane copolymer that blocks the trimethylsiloxy group at both ends of the molecular chain, the compound represented by the following formula, and further, a part or all of the methyl group in the following formula is an ethyl group, a propyl group, or a phenyl group. Examples thereof include compounds substituted with a trifluoropropyl group or the like.
_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3
(E in the equation is an integer of 1 or more, and f is an integer of 2 or more.)

Examples of the methylhydrogenpolysiloxane in which both ends of the molecular chain are silanol groups include a compound represented by the following formula, and a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like. Examples thereof include compounds substituted with.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H
(E in the formula is an integer of 1 or more.)

Examples of the methylhydrogenpolysiloxane that blocks the dimethylhydrogensiloxy group at both ends of the molecular chain include a compound represented by the following formula, and further, a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, or a trifluororo. Examples thereof include compounds substituted with a propyl group or the like.
_{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) e -Si (CH 3) 2 H
(E in the formula is an integer of 1 or more.)

The dimethylhydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain includes, for example, a compound represented by the following formula, and further, a part or all of the methyl group in the following formula is an ethyl group or a propyl group. Examples thereof include compounds substituted with a phenyl group, a trifluoropropyl group and the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H
(E and h in the equation are integers of 1 or more, respectively.)

The above compounds can be produced by known methods, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane, and hexamethyldisiloxane or 1,3-dihydro-1, which can be a terminal group. Compounds containing a triorganosilyl group or diorganohydrogensiloxy group, such as 1,3,3-tetramethyldisiloxane, are mixed with a compound containing a triorganosilyl group or a diorganohydrogensiloxy group in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, or methanesulfonic acid-10. It can be easily obtained by equilibrating at a temperature of about ° C. to + 40 ° C.

The amount of the hydrosilyl group-containing compound (Y) according to the present invention is usually 0.1 to 100 parts by weight, preferably 0.% by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (S). 1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, further 0.2 to 30 parts by weight, further 0.2 to 20 parts by weight, particularly 0.5 to 10 parts by weight, most preferably. It is used in a proportion of 0.5 to 5 parts by weight. It is not preferable to use the hydrosilyl group-containing compound (Y) in a proportion exceeding 100 parts by weight because it is disadvantageous in terms of cost.

<Platinum catalyst (Z)>
The platinum-based catalyst (Z) for hydrosilicon crosslinking used in the present invention is an addition reaction catalyst, and contains an alkenyl group contained in an ethylene / α-olefin / non-conjugated polyene copolymer (S) and a hydrosilyl group-containing compound (Y). ) Can be used without particular limitation as long as it promotes the addition reaction with the hydrosilyl group (hydrosilylation reaction of alkene).

The specific platinum-based catalyst may be a known one that is usually used for addition-curing type curing. For example, the fine powder metal platinum catalyst described in US Pat. No. 2,970,150, US Pat. No. 2, Ltd. , 823,218, Platinum Chloride Catalyst, US Pat. No. 3,159,601, US Pat. No. 3,159,662, US Pat. No. 3,159,662, US Pat. Complex compound of platinum chloride acid and olefin described in Japanese Patent No. 3,516,946, platinum described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780. Examples include a complex compound of vinyl siloxane and vinyl siloxane.

More specifically, a simple substance of platinum (platinum black), a platinum chloride acid, a platinum-olefin complex, a platinum-alcohol complex, or a carrier such as alumina or silica on which a platinum carrier is supported can be mentioned.

The amount of the platinum-based catalyst (Z) for hydrosilicon cross-linking is usually 0.1 to 100,000 ppm by weight, preferably 0.1 to 10000, based on the ethylene / α-olefin / non-conjugated polyene copolymer (S). It is used in a proportion of ppm by weight, more preferably 1 to 5000 ppm by weight, and particularly preferably 5 to 1000 ppm by weight. If it is less than 0.1 ppm by weight, the crosslinking rate tends to be slow, and if it is used at a ratio of more than 100,000 ppm by weight, it is disadvantageous in terms of cost, which is not preferable. When a platinum-based catalyst (C) for hydrosilicon cross-linking is used at a ratio within the above range, an ethylene / α-olefin / non-conjugated polyene copolymer that can form a cross-linked molded product having an appropriate cross-linking density and excellent strength characteristics and elongation characteristics can be formed. A coalesced composition is obtained.

<Reaction inhibitor (D)>
The reaction inhibitor (D) used in the present invention is a cross-linking reaction (to an alkene) between an alkenyl group of an ethylene / α-olefin / non-conjugated polyene copolymer (S) and a hydrosilyl group of a hydrosilyl group-containing compound (Y). Hydrosilylation addition reaction) is suppressed. Suppression of this cross-linking reaction is necessary in order to stabilize workability during kneading and molding.
The reaction inhibitor (D) used in the present invention is a compound represented by the general formula [III], and is a compound represented by the general formula [III].

〔式中、Ｒ¹およびＲ²は炭素数１〜４のアルキル基であり、同一でも異なってよい。具体的には、メチル基からブチル基であり、ｎ−、ｉｓｏ−、ｓｅｃ−、ｔｅｒｔ−などの異性体を含む。好ましくは、メチル基またはエチル基であり、特に好ましくは、メチル基である。Ｒ¹およびＲ²の組合せは、同一でも異なってよいが、好ましくは、メチル基とエチル基を含む場合であり、特に好ましくは、全てメチル基で同一である場合である。〕

[In the formula, R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, and may be the same or different. Specifically, it is a methyl group to a butyl group and contains isomers such as n-, iso-, sec- and tert-. It is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The combination of R ¹ and R ² may be the same or different, but is preferably a case where it contains a methyl group and an ethyl group, and particularly preferably a case where all the methyl groups are the same. ]

Specific examples of the general formula [III] are 3,7,11-trimethyl-3-hydroxy-1-dodecine, 3,7,11-triethyl-3-hydroxy-1-dodecine, 3,7,11-tri. Propyl-3-hydroxy-1-dodecin, 3,7,11-triisopropyl-3-hydroxy-1-dodecin, 3,7,11-tributyl-3-hydroxy-1-dodecin, 3,7,11-tri Isobutyl-3-hydroxy-1-dodecine, 3,7,11-tri-sec-butyl-3-hydroxy-1-dodecine, 3,7,11-tri-tert-butyl-3-hydroxy-1-dodecine,
3,7-Dimethyl-11-ethyl-3-hydroxy-1-dodecin, 3,7-dimethyl-11-propyl-3-hydroxy-1-dodecin, 3,7-dimethyl-11-butyl-3-hydroxy- Examples thereof include 1-dodecine and 3,11-dimethyl-7-ethyl-3-hydroxy-1-dodecine. Particularly preferred is 3,7,11-trimethyl-3-hydroxy-1-dodecine.

The amount of the reaction inhibitor (D) is usually 0.05 to 5 parts by weight, preferably 0.07 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (S). Parts, more preferably 0.07 to 4.5 parts by weight, still more preferably 0.1 to 4.5 parts by weight, particularly preferably 0.1 to 3.0 parts by weight, most particularly preferably 0.1 to 1 parts by weight. It is used in a proportion of 0.0 parts by weight. If it is less than 0.05 parts by weight, the cross-linking rate may be too fast, and if the reaction inhibitor (D) is used at a ratio of more than 5 parts by weight, the reaction suppressing effect may be large and cross-linking may be difficult to occur.

<Other compounding agents>
In addition to the above-mentioned essential compounding agents, the ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention may contain, if necessary, a reinforcing agent, an inorganic filler, a softening agent, and an antiaging agent (stable). Agent), processing aid, and foaming agent, foaming aid, plasticizer, colorant, other rubber compounding agent, rubber, resin, and the like can be blended as other components. The type and content of these compounding agents are appropriately selected according to the intended use, and among these, it is particularly preferable to use a reinforcing agent, an inorganic filler, a softening agent, or the like.

In the present invention, examples of the resin used as needed include general-purpose resins such as polyethylene, polypropylene, and polystyrene. Further, in the present invention, as the rubber used as needed, silicone rubber, ethylene / propylene random copolymer rubber (EPR), natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber and the like are blended. Can be used. Further, rubber (EPT) different from the above-mentioned copolymer (A) but similar to the above-mentioned copolymer (A), and even if the above-mentioned copolymers (A) are used together, a) ethylene / α-olefin having 3 to 20 carbon atoms. Two or more of the above-mentioned copolymers (A) having different molar ratios, (b) iodine values, or (c) ultimate viscosity [η] can be mixed and used. In particular, in (c), a mixture of a low limit viscosity component and a high limit viscosity component can be mentioned.

<Ethylene / α-olefin / non-conjugated polyene copolymer composition>
The ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention includes the ethylene / α-olefin / non-conjugated polyene copolymer (S), the hydrosilyl group-containing compound (Y), and the platinum-based catalyst. A composition comprising (Z) and a reaction inhibitor (D).
The preferred amount of each component contained in the ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention is as described above.

<Method for producing a molded product composed of an ethylene / α-olefin / non-conjugated polyene copolymer composition>
In the method for producing a molded product of the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer composition according to the present invention is melt-kneaded in a temperature range of usually 50 to 130 ° C., preferably 70 to 110 ° C. , Usually, is a method for producing a molded product, characterized in that the composition is crosslinked by injection molding in a mold set in a temperature range of 150 to 200 ° C., preferably 160 to 190 ° C.

In the method for producing a molded product of the present invention, the method of melt-kneading an ethylene / α-olefin / non-conjugated polyene copolymer composition is performed on an extrusion molding machine provided with the above-mentioned ethylene / α-olefin / non-conjugated. A predetermined amount of the polyene copolymer (S) or the like may be weighed and then melt-kneaded in the above temperature range, but after the above ethylene / α-olefin / non-conjugated polyene copolymer (S) or the like is weighed in a predetermined amount. , Banbury mixer, kneader, internal mixers such as intermix, may be melt-kneaded in advance and put into an injection molding machine.

Molds obtained from the ethylene / α-olefin / non-conjugated polyene copolymer composition of the present invention include, for example, hoses, rubber for tires, O-rings, industrial rolls, packings (for example, condenser packings), gaskets, and the like. Suitable for anti-vibration rubber, anti-vibration material or anti-vibration material (for example, engine mount, motor mount), muffler hanger, sponge (for example, heat insulating sponge, protective sponge, slightly foamed sponge), color skin material, paper feed roll, etc. Used. Among these, it is suitably used for interior / exterior parts for automobiles and applications requiring heat resistance, and is suitable for hoses, O-rings, packings, sponges, anti-vibration rubbers, and sponges.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
The physical characteristics of the ethylene / α-olefin / non-conjugated polyene copolymer used in Examples and Comparative Examples were measured by the following methods.

<Ethylene / α-olefin / non-conjugated polyene copolymer>
(1) Composition of ethylene / α-olefin / non-conjugated polyene copolymer The weight fraction (% by weight) of each constituent unit of the ethylene / α-olefin / non-conjugated polyene copolymer and the molar of ethylene and α-olefin The ratio was determined by the value measured by ^{13 C-NMR.} The measured values were measured using an ECX400P type nuclear magnetic resonance device (manufactured by JEOL Ltd.) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and an integration number of 8000 times. It was obtained by measuring the ¹³ C-NMR spectrum of the polymer.

(2) Extreme viscosity [η]
The ultimate viscosity [η] (dl / g) was measured using a fully automatic ultimate viscometer manufactured by Rigo Co., Ltd. at a temperature of 135 ° C. and a measurement solvent of decalin.

(3) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are polystyrene-equivalent numerical values measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. In addition, the molecular weight was calculated based on a conversion method by preparing a calibration curve using commercially available monodisperse polystyrene.
Equipment: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters),
Analytical device: Empourer2 (manufactured by Waters),
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (7.5 mm ID x 30 cm, manufactured by Tosoh Corporation),
Column temperature: 140 ° C,
Mobile phase: o-dichlorobenzene (containing 0.025% BHT),
Detector: Differential Refractometer (RI), Flow Velocity: 1.0 mL / min,
Injection volume: 400 μL,
Sampling time interval: 1s,
Column calibration: Monodisperse polystyrene (manufactured by Tosoh),
Molecular weight conversion: Old method EPR conversion / Calibration method considering viscosity.

(4) Complex viscosity η ^* and P value Using a viscous elasticity measuring device Ares (manufactured by Rheometric Scientific) as a leometer, the frequency is ω = 0.01 rad / s under the conditions of 190 ° C. and 1.0% strain. Complex Viscosity η ^* ₍ ω _{= 0.01)} , Complex Viscosity η ^* at Frequency ω = _{0.1 rad / s * (} ω _{= 0.1)} ^{, Complex Viscosity η * at} _{Frequency ω = 10 rad / s * (} ω _{= 10)} and Frequency ω The complex viscosity η ^* ₍ ω _{= 100) at = 100} rad / s (both units are Pa · sec) was measured.

Also, from the obtained results ^{, the P value (η *} ₍ ω _{= 0.1)} / η ^* ₍ ω), which is the ratio (η * ratio) of the complex viscosity of ^{η *} ₍ ω _{= 0.1)} and η ^* ₍ ω _{= 100). = 100)} ) was calculated.
The method for measuring the evaluation of the copolymer composition used in Examples and Comparative Examples is as follows.

[Appearance sensuality evaluation]
The copolymer composition was injection-molded under the following conditions, and the surface state of the obtained injection-crosslinked molded product was observed.
Molding conditions: 75t vertical injection (Matsuda Seisakusho), mold: spiral flow Nozzle temperature: 60 ℃
Mold temperature: 180 ℃
Injection speed 40 cm 3 / sec,
Molding pressure 135 kgf
Molding method: Manual (1) Sample filling 5 times thrown away (2) Mold tightening → Extruder OFF → Nozzle advance → Injection (stopwatch) → Nozzle retreat immediately → Mold open in a specified time * Because vulcanization is quick The limit is 3 or 4 times (vulcanization progresses inside the nozzle)

[Evaluation criteria]
1: The surface is smooth and glossy 2: Fine irregularities are observed 3: Remarkable irregularities are observed. There is no luster.
4: Remarkable molding defects such as breakage are observed in the molded body.

[Manufacturing Example 1]
A polymerization reaction of ethylene, propylene, and 5-vinyl-2-norbornene (VNB) was continuously carried out at 87 ° C. using a polymerizer having a volume of 300 L equipped with a stirring blade.
Hexane (feed amount: 32.6 L / h) was used as the polymerization solvent, and the ethylene feed amount was 3.6 kg / h, the propylene amount was 6.1 kg / h, and the VNB feed amount was 290 g / h. It was continuously supplied to the polymer so that the hydrogen feed amount was 6.3 NL / h.

Feed amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 87 ° C. It was continuously supplied to the polymerizer so as to be 0.0015 mmol / h. In addition, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ (CB-3) as a cocatalyst has a feed amount of 0.0075 mmol / h, and triisobutylaluminum (TIBA) as an organoaluminum compound has a feed amount of 20 mmol / h. Each was continuously supplied to the polymerizer so as to be.

In this way, a solution containing 15.2% by mass of an ethylene / propylene / VNB copolymer formed from ethylene, propylene and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, the ethylene / propylene / VNB copolymer was separated from the solvent by steam stripping treatment, and then the pressure was reduced at 80 ° C. for 24 hours. It was dry.

By the above operation, an ethylene / propylene / VNB copolymer (S-1) formed from ethylene, propylene and VNB was obtained at a rate of 4.7 kg / h.
The physical characteristics of the obtained copolymer (S-1) were measured by the method described above. The results are shown in Table 1.

[Manufacturing Example 2]
Using a stainless steel polymerizer having a substantially internal volume of 100 liters (stirring rotation speed = 250 rpm) equipped with stirring blades, ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene was continuously carried out. From the side of the polymer to the liquid phase 60 liters of hexane, 3.7 kg of ethylene, 8.0 kg of propylene, 1440 g of 5-vinyl-2-norbornene (VNB), 50 liters of hydrogen, catalyst VOCl3 was continuously supplied at a rate of 48 mmol, Al (Et) 2Cl was supplied at a rate of 240 mmol, and Al (Et) 1.5 Cl1.5 was continuously supplied at a rate of 48 mmol. The copolymerization reaction was carried out under the above conditions, and an ethylene / propylene / VNB copolymer (hereinafter, abbreviated as copolymer (A-1)) was obtained in a uniform solution state. The ethylene / propylene / VNB copolymer was separated from the solvent by steam stripping treatment, and then dried under reduced pressure at 80 ° C. for 24 hours.
The physical characteristics of the obtained copolymer (A-1) were measured by the method described above. The results are shown in Table 1.

[Examples 1 to 3]
As a first step, 100 parts by weight of the ethylene / propylene / VNB copolymer (S-1) obtained in Production Example 1 was kneaded for 1 minute using a Mixtron BB-4 type mixer (manufactured by Kobe Steel). Next, 40 parts by weight of carbon black (Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.), 30 parts by weight of heavy calcium carbonate (Whiten SB [manufactured by Shiraishi Calcium Co., Ltd.]), paraffin-based process oil (Diana) Process PW-380, 40 parts by weight of Idemitsu Kosan Co., Ltd., and 10 parts by weight of specially treated calcium oxide (Vesta PP [manufactured by Inoue Lime Industry Co., Ltd.]) were added and kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.

Next, as the second step, the compound obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 16 rpm, rear roll rotation speed 18 rpm), and a hydrosilyl group-containing compound (manufactured by Shin-Etsu Chemical Co., Ltd .: (CH3) 3SiO- (SiH (CH3) -O-) 6-Si (CH3) ) 2-O-Si (C6H6) 2-O-Si (CH3) 3) 4 parts by weight, platinum-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: platinum chloride acid + [CH2 = CH (Me) SiO] 4 complex) 0.2 part by weight and 0.1 part by weight of reaction inhibitor (manufactured by Shin-Etsu Chemical Co., Ltd .: ethyl-1-octin-3-ol) were added and kneaded for 10 minutes to form an uncrosslinked rubber compound (ethylene α-). An olefin / non-conjugated polyene copolymer composition) was obtained. Injection molding evaluation was performed using this rubber compound.

For injection molding, a spiral flow mold is attached to a 75t vertical mold injection (VI-75P (B) -40 / 60SPR5 (500) -P, manufactured by Matsuda Seisakusho), and the nozzle temperature is 60 ° C, the mold temperature is 180 ° C, and the injection speed is 40 cm. ^{Performed under the conditions of 3} / sec, mold clamping pressure 135 kgf, and vulcanization time (shown in the table), the flow length of the rubber compound (copolymer composition), and the appearance of the obtained molded product (crosslinked molded product). Evaluation was performed.
The results are shown in Table 2.

[Comparative Examples 1 to 3]
The same procedure as in Example 1 was carried out except that the copolymer (A-1) obtained in Production Example 2 was used instead of the ethylene / propylene / VNB copolymer (S-1) used in Example 1. ..
The evaluation results are shown in Table 3.

As is clear from Tables 2 and 3, the copolymer composition using the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention is described in Examples 1 to 3 [In Examples, As shown in [Copolymer (S-1)], in a copolymer composition using the ethylene / propylene / VNB copolymer shown in Comparative Examples 1 to 3 (hereinafter, copolymer (A-1)). In comparison, the flow length of the copolymer composition was 255 mm (Comparative Example 1) with respect to 325 mm (Example 1), 230 mm (Comparative Example 2) and 270 mm (Example 3) with respect to 280 mm (Example 2). It is as long as 225 mm (Comparative Example 3) and has excellent fluidity (injection moldability).

Further, the surface states of the crosslinked molded articles obtained in Examples 1 to 3 were excellent in that fine irregularities were observed (evaluation: 2), whereas they were obtained in Comparative Examples 1 to 3. As for the surface condition of the crosslinked molded product, if the molded product has remarkable molding defects such as breakage (evaluation: 4) or remarkable unevenness and no gloss (evaluation: 3), the surface condition is not good. It is clear that.

Further, as shown in Example 3, the copolymer composition using the ethylene / α-olefin / non-conjugated polyene copolymer (S) according to the present invention has a vulcanization time (crosslinking time) of 13 seconds. It is clear that a crosslinked molded article having a good surface condition can be obtained even if it is shortened, that is, one cycle in injection molding can be shortened.

Claims (3)

(1) A total of two partial structures selected from the group consisting of ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, and the following general formulas (I) and (II) in the molecule. It has a structural unit derived from the non-conjugated polyene (C) including the above.
Ethylene / α-olefin / non-conjugated polyene copolymer (S), which is characterized by satisfying the following requirements (i) to (v).
(2) Hydrosilyl group-containing compound (Y) having at least two hydrosilyl groups in one molecule,
(3) a platinum catalyst for hydrosilicon crosslinking (Z), and (4) ethyl-1-octyn-3-reaction inhibitor consisting ol,
A molded product characterized by containing an ethylene / α-olefin / non-conjugated polyene copolymer composition is melt-kneaded, injection-molded into a mold, and crosslinked in the mold. how to.

(I) The molar ratio of ethylene / α-olefin is 40/60 to 99.9 / 0.1.
(Ii) The weight fraction of the structural unit derived from the non-conjugated polyene (C) is 0.07% by weight to 10% by weight in 100% by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (S). is there.
(Iii) Weight average molecular weight (Mw) of ethylene / α-olefin / non-conjugated polyene copolymer (S) and weight fraction of structural unit derived from non-conjugated polyene (C) (weight fraction of (C)) (% By weight)) and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following formula (1).
4.5 ≤ Mw x (C) weight fraction / 100 / (C) molecular weight ≤ 40 ... Equation (1)
^{(Iv) Complex viscosity η *} ₍ ω _{= 0.1)} (Pa · sec) at frequency ω = 0.1 rad / s and frequency ω = obtained by linear viscous elasticity measurement (190 ° C.) using a leometer. ^{The ratio P (η *} ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ^{) to the complex viscosity η *} ₍ ω _{= 100)} (Pa · sec) at 100 rad / s, the ultimate viscosity [η], and the above. The weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≤ (C) x 6 ... Equation (2)
(V) The number of long chain branches per 1000 carbon atoms (LCB _1000C ) obtained by using 3D-GPC and the natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) are expressed by the following formula (3). Meet.
LCB _1000C ≦ 1-0.07 × Ln (Mw) ‥ (3) The ethylene-alpha-olefin-non-conjugated polyene copolymer composition, the ethylene-alpha-olefin-non-conjugated polyene copolymer (S): To 100 parts by weight of the hydrosilyl group-containing compound (Y) is 0.1 parts by weight, the platinum-based catalyst (Z) is from 0.1 to 100,000 wt ppm, and the molded article of claim 1 wherein the reaction inhibitor is in the range of 0.05 to 5 parts by weight How to manufacture. The method for producing a molded product according to claim 1 or 2, wherein the temperature at the time of melt-kneading is in the range of 50 to 130 ° C., and the temperature of the mold is in the range of 150 to 200 ° C.