Technical field
[0001]The present invention, laminates, and more particularly, to a laminate of a polar rubber and a non-polar rubber.
BACKGROUND
[0002]The industrial hose formed from rubber, strength, flexibility, heat resistance, flex resistance, various properties such as solvent resistance is required, one kind of difficult to satisfy all properties required in rubber it is. Therefore, it is laminated rubber having different properties is generally performed.
[0003]
When laminating a heterologous rubber, in the case of rubber having a polar but also be directly adhered to other rubbers, a method of adhering via an adhesive layer in the case of non-polar rubber is generally used.
The automobile engine around the rubber hose, heat aging resistance, fatigue resistance, and oil resistance are required at a high level. As the material of such hoses, conventionally, fluorine rubber, acrylonitrile-butadiene copolymer, acryl rubber, acrylate-ethylene copolymer, and silicone rubber is often used. However, in recent years, for the purpose of performance improvement and fuel efficiency in automobiles, the temperature in the engine room has been heated to a high temperature, under such circumstances, the engine around the rubber hose of an automobile, heat resistance, oil resistance, etc. it is required to further improve. Here, heat resistance, in terms of further improvement of oil resistance, etc., a fluorine rubber is the preferred, the fluorine rubber is expensive, there is a certain limit to the amount used in terms of cost. Therefore, conventionally, research and development of a laminate having a layer comprising a layer and a non-fluorine rubber made of a fluorine rubber has been variously conducted.
[0004]
One embodiment of such a laminate, the laminate is interposed an adhesive layer between the layer consisting of a layer and a non-fluorine rubber made of a fluorine rubber. Such laminates, for example, Patent Document 1, a polymer layer comprising a fluoropolymer, and a base material, a laminate obtained by bonding via a bonding layer comprising a fluoroelastomer is disclosed. Here, Patent Document 1, as a base material, in addition to the inorganic substrate and a fluoropolymer such as metal or inorganic glass, acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene monomer (EPM) rubber, ethylene propylene diene monomer (EPDM) rubber, it is described that can be used non-fluorinated elastomer such as epichlorohydrin (ECO) rubber.
[0005]
As another embodiment, a laminate and a layer comprising a layer and a non-polar rubber made of a fluorine rubber formed by vulcanization may be mentioned. For example, Patent Document 2, fluorine and a layer containing a rubber and vulcanizing agent and a layer containing a non-fluorine rubber and vulcanizing agents such as silicone rubber, is disclosed is bonded laminate by vulcanized adhesion there.
[0006]
Toward the fuel economy of automobiles, in recent years the engine down-sizing, is progressing turbo reduction. Turbocharged engine has a structure for feeding the engine to cool the air compressed by the compressor wheel charge air cooler, between the compressor wheel and charge air cooler are connected by a rubber hose. The turbocharger hose, high heat aging resistance because air passes through the high pressure and high temperature (about 180 ° C.) is obtained. Further, fatigue resistance to withstand the constant pressure vibration generated by the passage of air also required. In the current such applications, such as high an acrylic rubber and a silicone elastomer heat aging resistance is employed.
[0007]
On the other hand, nitrile rubbers such as acrylonitrile-butadiene rubber is excellent in oil resistance, wear resistance is good, and because it is relatively inexpensive, fuel hose, oil hose, widely applications requiring, such as oil-resistant oil seal It has been used. Further, hydrogenated nitrile rubber obtained nitrile rubber hydrogenated also sometimes used in similar applications.
[0008]
Patent Document 3, a composition containing an ethylene-alkyl acrylate copolymer and have been described cured product, cured product is vulcanizates, impact fatigue resistance and improved over conventional vulcanizate It has been described to exhibit heat resistance.
[0009]
Patent Document 4, excellent heat resistance and have a fatigue resistance, as to prevent the occurrence of inner layer cracking, with an innermost rubber layer made of fluorinated rubber, silicone rubber, acrylic rubber, ethylene acrylic rubber , epichlorohydrin rubber, turbo hoses and a skin layer due to hydrogenated nitrile rubber, as well as fastening structure formed by fastening the turbo hose pipe connecting portion has been proposed.
[0010]
On the other hand, a shaped body of non-polar rubbers such as ethylene-propylene-diene rubber (EPDM), adhesion of the molded body or the rubber molded product of the same type made of other materials such as metal or plastic, is generally the difficulty known It is. EPDM, because non-polar rubber, when stacking a method via an adhesive layer were common. For example, Patent Document 5, a rubber molded article, between the molded body made of rubber or other material, by disposing a layer obtained by crosslinking a particular adhesive comprising a EPDM with a crosslinking agent, It is described to obtain a rubber bonded object. The examples of Patent Document 5, the two EPDM sheets bonded by an adhesive comprising a EPDM with a crosslinking agent, the adhesive body is disclosed by crosslinking.
CITATION
Patent Document
[0011]
Patent Document 1: JP-T 2005-523181 Patent Publication
Patent Document 2: WO 2003/039858
Patent Document 3: JP-T 2009-500473 Patent Publication
Patent Document 4: JP 2013-221580 Patent Publication
Patent Document 5: JP 2014-162823 JP
Summary of the Invention
Problems that the Invention is to Solve
[0012]
The present invention, adhesion with difficult olefinic rubber of the non-polar or polar small other materials, and to provide a laminate of a rubber containing a Group 15 element is heterologous rubber.
Means for Solving the Problems
[0013]
The present inventors have intensively studied a result in such a situation, by using a specific adhesive resin, the adhesive is a difficult olefinic rubber of the non-polar or polar small other materials, 15th heterologous rubber found that laminates and a rubber containing a group element firmly to be integrated is obtained, and have completed the present invention.
[0014]
That is, the present invention relates to the following [1] to [10].
[1]
olefin rubber layer (A),
an ethylene-vinyl acetate copolymer, silane modified ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymers and ionomers, and ethylene-methacrylic acid copolymer and an adhesive resin layer (B) containing at least one element selected from the group consisting of an ionomer thereof,
and a layer (C) comprising a rubber containing a group 15 element
laminate comprising a structure which is formed by laminating in this order.
[0015]
[2]
The adhesive resin layer (B) is laminated body according to the containing one or more selected from the group consisting of ethylene-vinyl acetate copolymer and silane-modified ethylene-vinyl acetate copolymer [1].
[3]
the layer (C), the laminate according to the containing rubber containing a nitrogen atom [1] or [2].
[0016]
[4]
the layer (C), nitrile rubber, laminate according to any one of the comprising at least one element selected from the group consisting of hydrogenated nitrile rubber and urethane rubber [1] to [3].
[0017]
[5]
the layer (C), the laminated body according to any one of the containing nitrile rubber [1] to [3].
[0018]
[6]
The olefin-based rubber layer (A), said containing ethylene-alpha-olefin-nonconjugated polyene copolymer [1] to laminate according to any one of [5].
[0019]
[7]
The ethylene-alpha-olefin-non-conjugated polyene copolymer has a 5-vinyl-2-norbornene (VNB) derived constituent units of the laminate according to [6].
[0020]
[8]
hose having a laminate according to any one of [1] to [7], as at least one portion.
[0021]
[9]
for the automotive, motorcycle, industrial machinery, used in any of the applications for construction equipment or agricultural machinery, the hose according to [8].
[10]
and the layer (A) and the layer (C), comprising the step of adhering the said layer (B), wherein [1] to method for producing a laminate according to any one of [7].
The invention's effect
[0022]
According to the present invention, through an adhesive resin layer having a specific adhesive resin contains adhesion and difficult olefinic rubber of the non-polar or polar small other materials, a Group 15 element is heterologous Rubber Rubber preparative it is possible to provide a laminate which together firmly.
DESCRIPTION OF THE INVENTION
[0023]
[Laminate]
The laminate of the invention,
olefin-based rubber layer (A) (hereinafter sometimes referred to as "layer (A)".) And the
adhesive resin layer (B) (hereafter, referred to "the layer (B) it may be referred to as "a.)
a layer comprising a rubber containing a group 15 element (C) (hereinafter," layer (C) may be referred to as ".) and
is formed by laminating in this order including.
[0024]
Hereinafter, after describing the respective polymer constituting the layer (A) ~ layer (C), the method of described in detail laminate of the present invention.
olefin rubbers
olefin rubber used in the present invention is a rubber containing a constituent unit derived from an olefin as the main constituent unit. Examples of the olefin rubber, polyisobutylene, butyl rubber, ethylene · alpha-olefin copolymer rubber and the like, preferred examples of which include ethylene · alpha-olefin copolymer rubber.
[0025]
Examples of the ethylene-alpha-olefin copolymer rubber, an ethylene-alpha-olefin copolymer rubber and the ethylene-alpha-olefin-non-conjugated diene copolymer rubber and the like, ethylene-alpha-olefin-non-conjugated diene the copolymer rubber are preferable. Here, the ethylene-alpha-olefin-non-conjugated polyene copolymer has a constitutional unit derived from ethylene, a structural unit derived from an alpha-olefin, and a constituent unit derived from a nonconjugated polyene.
[0026]
Examples of the α- olefin, preferably α- olefin of 3 to 20 carbon atoms. The α- olefin, e.g., propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, and the like. Of these, propylene, 1-butene, 1-hexene, preferably α- olefin having 3 to 8 carbon atoms such as 1-octene, propylene is particularly preferred. Such alpha-olefins, the raw material cost is relatively inexpensive, shows the mechanical properties of ethylene-alpha-olefin-nonconjugated polyene copolymer obtained is excellent to obtain a laminate further having rubber elasticity the preferred because it can.
[0027]
Be used these α- olefins alone, it may be used in combination of two or more.
Specific examples of non-conjugated
polyene, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl 1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene chain non-conjugated dienes;
Norbornadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5-isobutenyl-2-norbornene, 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-f Seniru) -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, 5-vinylidene-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene unsaturated norbornene derivatives etc., methyl tetrahydroindene, and cyclic non-conjugated dienes of dicyclopentadiene, and the like;
2,3-diisopropyl Isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. trienes and 4-ethylidene-8-methyl-1,7-Nanojien the like.
[0028]
Be used these non-conjugated polyene is a type may be used in combination of two or more.
Of these nonconjugated polyenes, VNB and ENB are preferred.
[0029]
VNB has high availability, reactivity with the organic peroxide during the post-polymerization crosslinking reaction is good, the heat resistance of the laminate, is excellent in fatigue resistance. Thus, in one preferred embodiment of the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer has a constitutional unit derived from VNB. Ethylene-alpha-olefin-nonconjugated polyene copolymer, the structural units derived from VNB is ethylene-alpha-olefin-nonconjugated polyene copolymer in 100% by mass, it is 0.07 to 10 mass% preferably, more preferably 0.1 to 8.0 mass%, and most preferably 0.5 to 5.0 mass%.
[0030]
Further, ENB has high availability, the time of the crosslinking reaction after polymerization to highly reactive with sulfur and vulcanization accelerator, easily controlling the crosslinking rate, good mechanical properties can be easily obtained. Namely, in another preferred embodiment of the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer has a constitutional unit derived from ENB. Ethylene-alpha-olefin-nonconjugated polyene copolymer, the structural units derived from ENB is ethylene-alpha-olefin-nonconjugated polyene copolymer in 100% by mass, it is 0.07 to 10 mass% preferably, more preferably 0.1 to 8.0 mass%, and most preferably 0.5 to 5.0 mass%.
[0031]
Ethylene-alpha-olefin-nonconjugated polyene copolymer, it is preferable to satisfy at least one of the following requirements requirements (I) ~ (III), satisfies at least two requirements following requirement (I) ~ (III) it is more preferable, and particularly preferably satisfies the following requirements (I) ~ (III).
[0032]
Requirements (I): a structural unit derived from ethylene, the molar ratio of the constituent unit derived from an alpha-olefin (ethylene / alpha-olefin) is 40/60 to 99.9 / 0.1.
Requirements (II): constitutional unit derived from non-conjugated polyene, the ethylene-alpha-olefin-nonconjugated polyene copolymer in 100% by mass, 0.07 to 10 mass%.
Requirements (III): The intrinsic viscosity measured in a 135 ° C. decalin [eta] is 1.0 ~ 4.0dl / g.
[0033]
(Requirement (I))
requirements (I), the molar ratio of a structural unit derived from ethylene, the constitutional unit derived from alpha-olefin (ethylene / alpha-olefin) is 40/60 to 99.9 / 0. it is to identify that it is a 1.
[0034]
The molar ratio of a structural unit derived from ethylene, the constitutional unit derived from alpha-olefin (ethylene / alpha-olefin) is more preferably 55 / 45-85 / 15, 55 / 45-78 / 22 it is particularly preferred is.
[0035]
Wherein the ethylene / alpha-olefin is within the above range, obtained by crosslinking the ethylene-alpha-olefin-nonconjugated polyene copolymer, shows a rubber elasticity layer excellent comprising a crosslinked body, mechanical strength and it preferred to become excellent in softness. Also within this range, shows a rubber elasticity ethylene-alpha-olefin-nonconjugated polyene copolymer is excellent, preferable because of its excellent mechanical strength and flexibility.
[0036]
The molar ratio of a structural unit derived from ethylene of ethylene-alpha-olefin-nonconjugated polyene copolymer, a constituent unit derived from an alpha-olefin, 13 can be determined by C-NMR.
[0037]
(Requirement (II))
requirement (II) is a structural unit derived from a nonconjugated polyene, an ethylene-alpha-olefin-nonconjugated polyene copolymer in 100% by mass, is from 0.07 to 10 mass% it is intended to identify it.
[0038]
The amount of the constitutional unit derived from non-conjugated polyene, more preferably 0.1 to 8.0 mass%, and particularly preferably 0.5 to 5.0 mass%. Ethylene-alpha-olefin-non-conjugated polyene copolymer having a constituent unit derived from a nonconjugated polyene in the range has a sufficient hardness, preferably to become excellent in mechanical properties, a large crosslinking density it is possible to obtain a crosslinked body, preferably it is possible to increase the hardness of the layer composed of crosslinked product.
The amount of the constitutional unit derived from the non-conjugated polyene, 13 can be determined by C-NMR.
[0039]
(Requirement (III))
requirement (III) is ethylene-alpha-olefin-nonconjugated polyene copolymer, the intrinsic viscosity measured in a 135 ° C. decalin [eta] in the 1.0 ~ 4.0 dl / g it is intended to identify that.
[0040]
The intrinsic viscosity [eta] is more preferably 1.5 ~ 4.0dl / g. Preferable intrinsic viscosity balanced processability and physical properties to be within the range is favorable.
The intrinsic viscosity can be measured by the method described in Examples.
The ethylene-alpha-olefin-nonconjugated polyene copolymer, in addition to the above requirements (I) ~ (III), preferably satisfies the following requirements (IV).
[0041]
(Requirement (IV))
requirements (IV) are those of ethylene-alpha-olefin-nonconjugated polyene copolymer, B value represented by the following formula (i), to identify that this is 1.20 or more it is.
B value = ([EX] +2 [Y ]) / [2 × [E] × ([ X] + [Y]) ] · · (i)
[where [E], [X] and [Y] is , respectively, ethylene, alpha-olefin, and shows the mole fraction of the non-conjugated polyene, showing the [EX] ethylene -α- olefin diad chain fraction. ]
[0042]
B value is more preferably 1.20 to 1.40 and particularly preferably 1.20 to 1.25.
Within B value above range, the ethylene-alpha-olefin-nonconjugated polyene copolymer shows a small compression set at low temperature is preferred because an excellent balance between tensile strength of rubber elasticity and cold at low temperatures .
[0043]
And the B value of the ethylene-alpha-olefin-nonconjugated polyene copolymer is 1.20 or more, and the non-conjugated polyene is in VNB, the laminate of the present invention tend to particularly excellent in fatigue resistance, preferred .
[0044]
Incidentally, B value is an index indicating the randomness of the copolymerized monomer sequence distribution in the copolymer, in the formula (i) [E], [ X], [Y], [EX] is 13 C-NMR spectrum was measured, J. C. Randall [Macromolecules, 15, 353 ( 1982)], J. Ray [Macromolecules, 10, 773 ( 1977)] can be determined based on these reports.
[0045]
Incidentally, alpha-olefin of the ethylene-alpha-olefin-non-conjugated polyene copolymer (content of constituent units derived from the alpha-olefin), the non-conjugated polyene content (content of structural units derived from nonconjugated polyene) is , 13 can be determined by C-NMR.
[0046]
Ethylene-alpha-olefin-nonconjugated polyene copolymer, the range has ethylene as described above, and alpha-olefin, the structural units derived from the nonconjugated polyene, which does not impair the effects of the present invention, other monomer may have a structure unit derived from (ethylene, alpha-olefin, and monomers other than non-conjugated polyene). Constituent units derived from other monomers, ethylene-alpha-olefin-nonconjugated polyene copolymer in 100% by mass, preferably at most 30 mass%, more preferably at most 25 mass%, 20 mass % by particularly preferably less. Other monomers styrene, vinyl acetate, and the like.
[0047]
The ethylene-alpha-olefin-non-conjugated polyene copolymer has a weight average molecular weight (Mw) of preferably 10,000 to 600,000, more preferably 30,000 to 500,000, more preferably 50,000 ~ it is 400,000. Ethylene-alpha-olefin-nonconjugated polyene copolymer, the molecular weight distribution (Mw / Mn), preferably from 1.8 to 30, more preferably from 1.8 to 25.0, more preferably from 2.0 to 20 it is a .0. Incidentally, Mw and Mw / Mn can be determined as a numerical value in terms of polystyrene measured by gel permeation chromatography (GPC).
[0048]
For example, the laminate of the present invention, when subjected to heat resistance hose applications such as turbocharger hoses for automobiles, can be preferably used a relatively high molecular weight ethylene-alpha-olefin-nonconjugated polyene copolymer, Specifically, the weight average molecular weight (Mw) can be preferably used ethylene-alpha-olefin-nonconjugated polyene copolymer 100,000 to 600,000.
[0049]
(Requirement (V-i) ~ (V -iii))
parts ethylene-alpha-olefin-nonconjugated polyene copolymer, a non-conjugated polyene, selected from the group consisting of the following general formula (I) and (II) nonconjugated polyene containing two or more in the molecular structure in total (hereinafter, "specific non-conjugated polyene") if it contains, in addition to the above requirements (I) ~ (III), the following requirements (V-i) ~ ( preferably satisfies the V-iii).
[0050]
The weight average molecular weight of (V-i) ethylene-alpha-olefin-non-conjugated polyene copolymer (Mw), specific non-mass fraction of conjugated polyene derived constituting units (mass fraction of a specific non-conjugated polyene (mass and%)), the molecular weight of the specific non-conjugated polyene and (molecular weight of the specific non-conjugated polyene), but satisfy the following formula (1).
4.5 ≦ Mw × specific nonconjugated polyene mass fraction / 100 / specific non-conjugated polyene molecular weight ≦ 40 ... (1)
[0051]
(V-ii) obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, frequency omega = complex viscosity at 0.1 rad / s eta * ( omega = 0.1) (Pa · sec) and the frequency omega = complex viscosity at 100Rad / S Ita * ( Omega = 100) (Pa · Sec) the ratio of the P (Ita * ( Omega = 0.1) / Ita * ( Omega = 100) and), and the intrinsic viscosity [η], mass fraction of building blocks derived from the specific non-conjugated polyene and (mass fraction of a specific non-conjugated polyene), but satisfy the following formula (2).
P / ([eta] 2.9 ) ≦ specific nonconjugated polyene mass fraction × 6 ... (2)
[0052]
(V-iii) obtained by using the 3D-GPC, 1000 long chain branches per carbon atoms (LCB 1000 C- and), the natural logarithm [Ln (Mw)] and the following formula having a weight average molecular weight (Mw) ( 3) meet.
LCB 1000C ≦ 1-0.07 × Ln (Mw) ... (3)
[0053]
[Of 21]
[0054]
«Requirements (V-i)»
Requirements (V-i), in the ethylene-alpha-olefin-nonconjugated polyene copolymer, the weight average molecular weight of the ethylene-alpha-olefin-non-conjugated polyene copolymer (Mw) of the polymer When the mass fraction of the constituent unit derived from a specific nonconjugated polyene in the ethylene-alpha-olefin-non-conjugated polyene copolymer (mass fraction of a specific non-conjugated polyene: mass%) and the molecular weight of the specific non-conjugated polyene and (molecular weight of the specific non-conjugated polyene) but is to specify that satisfies the above formula (1). The above formula requirements (V-i) (1), it is preferably the following formula (1 ').
4.5 ≦ Mw × specific nonconjugated polyene mass fraction / 100 / specific non-conjugated polyene having a molecular weight of ≦ 35 ... (1 ')
[0055]
The ethylene-alpha-olefin-nonconjugated polyene copolymer, by satisfying the requirements (V-i), a suitable content of structural units derived from a particular non-conjugated polyene, exhibited sufficient crosslinking performance, excellent in crosslinking rate, it is possible to produce a laminate exhibiting excellent mechanical properties. The weight average molecular weight of the ethylene-alpha-olefin-non-conjugated polyene copolymer (Mw) can be determined as a numerical value in terms of polystyrene measured by gel permeation chromatography (GPC).
[0056]
In the ethylene-alpha-olefin-nonconjugated polyene copolymer, if it meets the "Mw × specific nonconjugated polyene mass fraction / 100 / molecular weight of the specific non-conjugated polyene" is the formula (1) or (1 ') about crosslinking becomes appropriate, and the mechanical properties and thermal aging resistance can be produced in good balance good laminate. When the value of the "molecular weight Mw × specific non-conjugated polyene mass fraction / 100 / specific non-conjugated polyene" is too low, the crosslinking is insufficient may be crosslinking rate becomes slow, and if said value is too high , the mechanical properties are deteriorated caused excessive crosslinking.
[0057]
«Requirements (V-ii)»
Requirements (V-ii) is of the ethylene-alpha-olefin-nonconjugated polyene copolymer is obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, frequency ω = 0.1rad / s complex viscosity at Ita * ( Omega = 0.1) (Pa · Sec) and, frequency ω = 100rad / s complex viscosity at Ita * ( Omega = 100) (Pa · Sec) the ratio of the P (eta * ( omega = 0.1) / eta * ( omega = 100) and), and the intrinsic viscosity [eta], the mass fraction of the constituent unit derived from the specific non-conjugated polyene (mass fraction of a specific non-conjugated polyene: wt%), but is to specify that satisfies the above expression (2). The above formula requirements (V-ii) (2), it is preferably the following formula (2 ').
P / ([eta] 2.9 ) ≦ specific nonconjugated polyene mass fraction × 5.7 ... (2 ')
[0058]
Here, the complex viscosity eta at frequency = 0.1 rad omega / s * ( omega = 0.1) and the frequency omega = 100 rad / s complex viscosity at eta * ( omega = 100) and the ratio of P (eta * ( omega = 0.1) / eta * ( omega = 100) ) is a representative of a frequency dependence of the viscosity, P / ([eta] corresponds to the left side of the equation (2) 2.9 ) is such as short-chain branching and molecular weight although effects may tend to exhibit a higher value when long chain branching is large. Generally, the ethylene-alpha-olefin-nonconjugated polyene copolymer, the more rich the constitutional unit derived from non-conjugated polyene, tend rich in long chain branching, ethylene-alpha-olefin used in the present invention · nonconjugated polyene copolymer by less long chain branching than conventional ethylene-alpha-olefin-nonconjugated polyene copolymer is believed to be able to satisfy the above expression (2).
[0059]
In the present invention, P value, using a viscoelasticity measuring apparatus Ares (Rheometric Scientific Inc.), 190 ° C., strain of 1.0%, was determined by performing measurements under the conditions of varying frequency, the complex viscosity at 0.1 rad / s If, from the complex viscosity at 100 rad / s, the ratio (eta * is obtained to determine the specific). Incidentally, the intrinsic viscosity [eta] denotes the measured values in the 135 ° C. decalin.
[0060]
«Requirements (V-iii)»
Requirements (V-iii), the above ethylene-alpha-olefin-nonconjugated polyene copolymer, long chain branching number of 1000 per carbon atoms obtained with 3D-GPC ( LCB 1000 C- a), natural logarithm [Ln (Mw)] of the weight average molecular weight (Mw) and but is to specify that satisfies the above equation (3). The above formula requirements (v) (3) is preferably the following formula (3 ').
[0061]
LCB 1000 C- ≦ 1-0.071 × Ln (Mw) ... (3 ')
by the above formula (3) or (3'), per unit number of carbon atoms in the ethylene-alpha-olefin-nonconjugated polyene copolymer length the upper limit of chain branching content is identified.
By ethylene-alpha-olefin-non-conjugated polyene copolymer satisfies the requirements (V-iii), less the proportion of long-chain branches contained, together with the excellent curing properties in the case of performing crosslinking using a peroxide , it is possible to obtain a laminate having excellent heat aging resistance.
[0062]
Here, Mw and 1000 long chain branches per carbon atoms (LCB 1000 C- ) can be determined by structural analysis using a 3D-GPC. As used herein, specifically, it was determined as follows.
[0063]
3D- using a high-temperature GPC apparatus PL-GPC220 type (Polymer Laboratories, Inc.), the absolute molecular weight distribution was determined intrinsic viscosity viscometer simultaneously. The main measurement conditions are as follows.
Detector: differential refractometer / GPC device embedded
2-angle light scattering photometer PD2040 type (Precison Detectors Ltd.)
bridge viscometer PL-BV400 type (Polymer Laboratories Ltd.)
Column: TSKgel GMH HR -H (S) HT × 2 this TSKgel GMH + HR -M (S) one ×
(both one per inner diameter 7.8Mmfai × length 300 mm)
temperature: 140 ° C.
mobile phase: 1,2,4-trichlorobenzene (0.025% BHT content)
injection The amount: 0.5 mL
sample concentration: ca 1.5 mg / mL
sample filtration: filtration with a pore diameter 1.0μm sintered filter
[0064]
In the above, dn / dc values required for the determination of the absolute molecular weight than the response intensity of the differential refractometer per a unit injection mass dn / dc value 0.053 of the standard polystyrene (molecular weight 190000) was determined for each sample.
Were calculated long chain branching parameter g'i of each eluted component from the relation of the absolute obtained from the intrinsic viscosity and light scattering photometer obtained from the viscometer molecular weight from the following equation (v-1).
[0065]
[Equation 1]
Here, [eta] = KM v ; applying the v = 0.725 relation.
Further, the following formula each mean value as g '(v-2), (v-3), was calculated from (v-4). Incidentally, Trendline was assumed to have a short chain branching only was determined for each sample.
[0066]
[Number 2]
[0067]
Further using G'w, branch points BrNo per molecular chain, long chain branching number LCB per 1000 carbon 1000C was calculated per unit molecular weight branching degree lambda. BrNo calculation formula of Zimm-Stockmayer (v-5) , also, LCB 1000 C- calculation of the λ the following formula (v-6), was used (v-7). g is the long chain branching parameter obtained from the inertial radius Rg, simple correlation follows have been made between the g 'determined from the intrinsic viscosity. The ε in the formula various values depending on the form of the molecule has been proposed. Here it was calculated assuming epsilon = 1 (i.e. g '= g).
[0068]
[Number 3]
lambda = BRNO / M ...
(V-6) LCB 1000 C- = lambda × 14000 ... (V-7)
wherein (V-7), "14000" is methylene (CH 2 of 1000 minutes in) units It represents the molecular weight.
[0069]
In the present invention, the specific non-conjugated polyene preferably includes VNB, the specific non-conjugated polyene and more preferably VNB.
[0070]
Process for producing an olefin-based rubber
manufacturing method of the olefin rubber is not particularly limited and may be a conventionally known method.
Here, as described above, in a preferred embodiment of the present invention, the olefin rubber are the ethylene-alpha-olefin-nonconjugated polyene copolymer, which will be described as an example.
[0071]
Ethylene-alpha-olefin-non-conjugated polyene copolymer used in the present invention, any production method may be prepared by, but is obtained by copolymerizing monomers in the presence of a metallocene compound it is preferable, it is more preferably obtained by copolymerization of monomers in the presence of a catalyst system comprising a metallocene compound.
[0072]
(Metallocene compound)
Ethylene-alpha-olefin-nonconjugated polyene copolymer, preferably in the presence of at least one metallocene compound selected from the compounds represented by the following general formula [A1], copolymerizing a monomer it is desirable to those obtained. The copolymerization of the monomers, if performed with a catalyst system comprising the metallocene compounds, long chain branching can be suppressed copolymer obtained contains, ethylene-alpha-olefin-nonconjugated polyene copolymer it can be readily prepared.
[0073]
Formula 1]
In the formula [A1], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a silicon shows the hetero atom-containing groups other than containing group, R 1 ~ R 4 two groups adjacent to each other out of may be bonded to each other to form a ring.
[0074]
The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, 6 to 20 carbon atoms and aryl (aryl) groups, or substituted aryl (aryl) groups. For example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, allyl (allyl) group, n- butyl group, isobutyl group, sec- butyl group, t- butyl group, amyl group, n- pentyl group, a neopentyl group , n- hexyl, n- heptyl, n- octyl, n- nonyl, n- decanyl group, 3-methylpentyl group, 1,1-diethyl propyl group, 1,1-dimethylbutyl group, 1- methyl-1-propyl butyl group, 1,1-propyl butyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, a phenyl group, o- tolyl group, m- tolyl group, p- tolyl group, xylyl group, isoproterenol Butylphenyl group, t- butyl phenyl group, a naphthyl group, a biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, a benzyl group, and a cumyl group.
[0075]
The hydrocarbon group may have a hydrogen atom substituted with a halogen atom, for example, can be mentioned a trifluoromethyl group, trifluoromethylphenyl group, pentafluorophenyl group, etc. chlorophenyl group.
[0076]
Examples of the silicon-containing group, a silyl group, siloxy group, hydrocarbon-substituted silyl group, etc. can be mentioned hydrocarbon-substituted siloxy group. For example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethyl silyl group, a triphenylsilyl group, dimethylphenylsilyl group, dimethyl -t- butylsilyl group, dimethyl (pentafluorophenyl ), such as a silyl group can be mentioned.
[0077]
The hetero atom-containing groups other than silicon-containing group, a methoxy group, an ethoxy group, an oxygen-containing group such as a phenoxy group, a nitro group, a cyano group, N- methylamino group, N, N- dimethylamino group, N- phenylamino can be exemplified nitrogen-containing groups such as groups, Borantoriiru group, a boron-containing group such as Jiboraniru group, a sulfonyl group, and sulfur-containing groups such as a phenyl group.
[0078]
R 6 and R 11 is a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R 7 and R 10 are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R 6 and R 7 may bond to each other to form a ring, R 10 and R 11 may be bonded to each other to form a ring. However, R 6 , R 7 , R 10 and R 11 are not are all hydrogen atoms.
R 13 and R 14 each independently represent an aryl group.
M 1 represents a zirconium atom.
Y 1Represents a carbon atom or a silicon atom.
[0079]
Q is a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, conjugated or nonconjugated diene neutral having 4 to 20 carbon atoms, a neutral ligand capable of coordination by an anionic ligand or a lone pair shown, j is an integer of 1-4, a plurality of Q if j is an integer of 2 or more may be the same as or different from each other.
[0080]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- propyl group, an isopropyl group, a 2-methylpropyl group, 1,1-dimethylpropyl group , 2,2-dimethylpropyl group, 1,1-diethyl propyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-methylpropyl group, sec- butyl group, t- butyl group, 1,1-dimethylbutyl group, 1,1,3-trimethyl butyl group, a neopentyl group, a cyclohexylmethyl group, a cyclohexyl group, 1-methyl-1-cyclohexyl group, a benzyl group and the like, preferably methyl group, ethyl group, a benzyl group.
[0081]
Examples of the halogenated hydrocarbon group, preferably a halogenated hydrocarbon group of 1 to 10 carbon atoms, specifically, a trifluoromethyl group, trifluoromethylphenyl group, pentafluorophenyl group, chlorophenyl group and the like.
[0082]
The conjugated or non-conjugated diene neutral having 4 to 20 carbon atoms, conjugated or nonconjugated diene neutral having 4 to 10 carbon atoms are preferred. Specific examples of the conjugated or nonconjugated diene neutral, s- cis - or s- trans eta 4 -1,3-butadiene, s- cis - or s- trans eta 4 -1,4-diphenyl - 1,3-butadiene, s- cis - or s- trans eta 4 -3-methyl-1,3-pentadiene, s- cis - or s- trans eta 4 -1,4-dibenzyl-1,3 butadiene, s- cis - or s- trans eta 4 -2,4-hexadiene, s- cis - or s- trans eta 4 -1,3-pentadiene, s- cis - or s- trans eta 4 - 1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta 4 -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.
[0083]
Examples of the anionic ligands, methoxy, t-butoxy, alkoxy group, phenoxy, acetate, carboxylate groups benzoate etc., mesylate, etc. sulfonate groups tosylate, and the like.
[0084]
Specific examples of the neutral ligands capable of coordination by lone pair, trimethylphosphine, triethylphosphine, triphenylphosphine, organic phosphorus compounds such as diphenyl methyl phosphine or tetrahydrofuran, diethyl ether, dioxane, 1,2 ethers such as dimethoxyethane.
[0085]
Substituents R in the formula [A1] 1 R from 4 The cyclopentadienyl group having, R 1 from R 4 unsubstituted cyclopentadienyl group is a hydrogen atom, 3-t-butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilyl cyclopentadienyl group, 3-phenyl-cyclopentadienyl group, 3-adamantyl-cyclopentadienyl group, 3-amyl cyclopentadienyl group, 3-cyclohexyl 3 of 1-substituted cyclopentadienyl groups such as cyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethyl-cyclopentadienyl group, 3-phenyl 5-methylcyclopentadienyl group, 3,5-di -t- butyl cyclopentadienyl group, 3,5-dimethyl-cyclopentadienyl Group, 3-phenyl-5-methylcyclopentadienyl group, 3-trimethylsilyl-5-methylcyclopentadienyl such 3,5-position 2 substituted cyclopentadienyl groups such as cyclopentadienyl group can be exemplified, but this shall is not. Ease of synthesis of the metallocene compounds, from the viewpoint of copolymerization capability of manufacturing cost and a non-conjugated polyene, unsubstituted (R 1 ~ R 4 cyclopentadienyl group is preferably a hydrogen atom) it is.
[0086]
Substituents R in the formula [A1] 5 R from 12 The fluorenyl group having the 2-methyl-fluorenyl group, 2-t-butyl-fluorenyl group, 2-position 2 monosubstituted such as phenyl fluorenyl group fluorenyl group, 4-methyl fluorenyl group, 4-t-butyl-fluorenyl group, 4-position mono-substituted fluorenyl group such as 4-phenyl fluorenyl group or 2,7-di -t- butyl-fluorenyl, group, 3,6-di -t- butyl-fluorenyl 2,7-position or 3,6-position disubstituted fluorenyl group such group, 2,7-dimethyl-3,6-di -t- butyl-fluorenyl group , 2,3,6,7-position 4-substituted fluorenyl group such as 2,7-diphenyl-3,6-di -t- butyl-fluorenyl group or the following general formula, [V-I], [ V-II] R, as represented in 6 and R 7 bound to form a ring with each other, 10 and R 11 is and bonded 2,3,6,7-position 4-substituted fluorenyl group which forms a ring are exemplified together, not limited.
[0087]
[Formula 2]
[0088]
[Formula 3]
formula [V-I], in [V-II], R 5 , R 8 , R 9 , R 12 are the same as defined in the general formula [A1],
R a , R b , R c , R d , R e , R f , R g and R h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, to form a ring together with adjacent substituents it may be. Examples of the alkyl group include exemplified a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, t- butyl group, amyl group, a n- pentyl group. In the formula [V-I], R x and R y are each independently a hydrocarbon group which may have an unsaturated bond having 1 to 3 carbon atoms, R x is R a or R c is may form a jointly double bond and bonded carbon, R y is R e or R g may form a double bond in cooperation with the carbon to which is bonded, R x and R y is preferably both are hydrocarbon groups, saturated or unsaturated having 1 or 2 carbon atoms.
[0089]
As the above-mentioned general formula [V-I] or compound represented by [V-II], specifically, the formula [V-III] represented by octamethyloctahydrodibenzofluorenyl group, the formula [V- tetramethyl dodeca hydro-dibenzo fluorenyl group represented by IV], octamethyl-tetrahydrodicyclopentadiene fluorenyl group represented by the formula [V-V], hexamethyl-dihydro represented by the formula [V-VI] dicyclopentanyl fluorenyl group, b of the formula [V-VII], h- dibenzo fluorenyl group.
[0090]
[Chemical Formula 4]
[0091]
[Formula 5]
[0092]
[Formula 6]
[0093]
[Chemical Formula 7]
[0094]
[Formula 8]
[0095]
Metallocene compound represented by the general formula [A1] containing these fluorenyl group is excellent in the copolymerization ability of any non-conjugated polyene, Y 1 when it is a silicon atom, 2,7-position disubstituted fluorenyl group, 3,6-position disubstituted fluorenyl group, 2,3,6,7-position 4-substituted fluorenyl group, a transition metal having a 2,3,6,7-position 4-substituted fluorenyl group represented by the general formula [V-I] compounds are particularly excellent. When Y is a carbon atom, R 5 a R 12 unsubstituted fluorenyl group is a hydrogen atom, 3,6-position disubstituted fluorenyl group, 2,3,6,7-position 4-substituted fluorenyl group, the general formula [V metallocene compounds having a 2,3,6,7-position 4-substituted fluorenyl group represented -I] is particularly excellent.
[0096]
In the present invention, in the metallocene compound represented by the general formula [A1], Y 1 in the silicon atom, R 5 a R 12 when until it is all a hydrogen atom, R 13 and R 14 is methyl group, butyl group, a phenyl group, silicon-substituted phenyl group, a cyclohexyl group, selected from the group other than a benzyl group;
Y 1 in the silicon atom, R 6 and R 11 are are both t- butyl group, R 5 , R 7 , R 8 , R 9 , R 10 , R 12 if is not t- butyl group, R 13 and R 14 is a benzyl group, selected from groups other than silicon-substituted phenyl
group; Y 1 is a carbon atom, R 5 R from 12 If all is a hydrogen atom, R 13 , R 14 is a methyl group, an isopropyl group, t- butyl group, an isobutyl group, a phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, a 4-biphenyl group, p- tolyl group, a naphthyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, selected from groups other than xylyl;
Y 1 is a carbon atom, R 6 and R 11 There t- butyl group is a common group selected from methyl or phenyl group, R 5 , R 7 , R 8 , R 9 , R 10 and R 12 when the are different groups or atoms, R 13 , R 14 is selected from methyl group, phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, a group other than a benzyl group;
Y 1In but carbon atoms, R 6 is dimethylamino group, a methoxy group or a methyl group, R 5 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are, R 6 in the different groups or atoms If so, R 13 , R 14 is a methyl group, selected from the group other than a phenyl group;
Y 1 is a carbon atom, a fluorenyl group and R 5 ~ R 12 are sites consisting of, b, h- dibenzofluorenyl Oreniru or a, if an i- dibenzo fluorenyl, R 13 , R 14 is preferably selected from methyl, group other than a phenyl group.
[0097]
Hereinafter, specific examples of the metallocene compounds represented by the general formula [A1] in the present invention, nor is it particularly limited in the scope of the invention thereby.
Specific examples of the metallocene compounds represented by the general formula [A1] in the present invention,
in the case Y is a silicon atom,
diphenylsilylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl ) zirconium dichloride,
diphenylsilylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di - t- butyl fluorenyl) zirconium dichloride,
diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
diphenylsilylene (cyclopentadienyl) ( octamethyloctahydrodibenzofluorenyl) zirconium dichloride De,
diphenylsilylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
diphenylsilylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
diphenylsilylene (cyclopenta dienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopenta dienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) ( 2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di p- tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl ) zirconium dichloride,
di (p- tolyl) silylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3 , 6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride ,
di (m-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Jill Niumujikurorido,
di (m-tolyl) silylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene full Oreniru) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (m-tolyl) silylene (cyclopentadienyl) (b, h - dibenzo fluorenyl) zirconium dichloride, and the like.
[0098]
In the case Y is a carbon atom,
diphenylmethylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3, 6-di -t- butyl-fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopenta dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (octamethyltetrasiloxane arsenide Logistics cyclopentadienyl fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) (3,6 - di -t- butyl fluorenyl) zirconium dichloride,
Di (p- tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) ( 2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di ( p- tolyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride ,
di (p- tolyl) methylene (cyclopentadienyl Le) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p- tolyl) methylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (m-tolyl) methylene ( cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (m-tolyl) methylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) methylene (cyclo pentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) methylene (cyclopentadienyl) ( 2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di ( m- tolyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (m- tolyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride ,
di (m-tolyl) methylene (cyclopentadienyl Le) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (m-tolyl) methylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (p-t-butylphenyl ) methylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3, 6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro dibenzo fluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclo pentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p-t-butylphenyl) methylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (4 - biphenyl Le) methylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (3,6-di -t- Buchirufuru Oreniru) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene ( cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl ) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (4-biphenyl) methylene (cyclopentadienyl) (b, h- dibenzofluorenyl Oreniru) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (2,7-di -t- Buchirufu Oreniru) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p- chlorophenyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (p- chlorophenyl) methylene (cyclopentadienyl) (b, h- dibenzofluorenyl Oreniru) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7 -T- butyl fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclo pentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6 - di -t- butyl fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (m-chlorophenyl) methylene (cyclopentadienyl) (b, h- dibenzofluorenyl Oreniru) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentyl Tajieniru) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyl octa hydro dibenzo fluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyl tetrahydrodicyclopentadiene cyclopentadienyl fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (m-trifluoromethylphenyl) methylene ( cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di -t- butyl-fluorenyl) zirconium dichloride,
di 2-naphthyl) methylene (cyclopentadienyl) (3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3, 6-di -t- butyl-fluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di -t- butyl-fluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (tetramethyl-dodeca hydro-dibenzo fluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (hexamethyl dihydrodicyclopentadiene fluorenyl ) zirconium dichloride,
di (2-naphthyl) methylene (cyclopentadienyl) (b, h- dibenzo fluorenyl) zirconium dichloride, and the like.
[0099]
As an example of the structure of these metallocene compounds, di (p- tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (below (A1-1)), and di (p - the structural formula of chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (below (A1-2)) below.
[0100]
[Formula 9]
The above compounds may be used alone or in combination of two or more.
[0101]
Can be suitably used in the preparation of the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention, the metallocene compound represented by the formula [A1] is prepared by any method without particular limitation be able to. Specifically, for example, J. Organomet. Chem. , 63,509 (1996), the applicant WO2005 / one hundred thousand four hundred ten publication is a publication relating to applications by, WO2006 / 123759, JP-WO01 / 27124, JP 2004-168744 and JP Patent Application 2004-175759 , it can be produced according to the method described JP 2000-212194 and the like.
[0102]
(Catalyst comprising a metallocene compound)
As the polymerization catalyst which can suitably used in the production of the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention comprises a metallocene compound represented by the formula [A1] mentioned above , those copolymerizable monomers.
[0103]
Preferably,
(a) and the metallocene compound represented by the general formula
[A1], (b) (b-1) organometallic compound, (b-2) an organoaluminum oxy-compound, and (b-3) wherein the metallocene reacts with compound (a) to form an ion pair compound, and at least one compound selected from,
if necessary,
include a catalyst composed of (c) and particulate carrier.
[0104]
It will be specifically described respective components.
((B-1) organometallic compound)
as (b-1) organometallic compound used in the present invention, the following formula is specifically [VII] ~ periodic table first and second group, such as [IX] and organometallic compounds of 12, 13 group is used.
[0105]
(B-1a) formula R a m Al (OR b ) n H p X q ‥ [VII]
(In the formula [VII], R a and R b may be the same or different from each other, the number of carbon atoms There 1-15, preferably a hydrocarbon group of 1 ~ 4, X is a halogen atom, m is 0
layers constituting the laminate of the present invention (A) an olefin-based rubber layer, i.e., a layer containing an olefin-based rubber described above.
[0184]
Here, the layer (A) is not preclude that a layer consisting of only olefin based rubber, usually well olefin rubber, with other components as a starting material, a layer made is there. Layer (A) is usually used an olefin-based rubber, a layer made by crosslinking. As a component other than olefin rubber such, (X-1) organic peroxides, (X-2) carbon black, (X-3) Antioxidant, (X-4) softener, (X-5 ) metal oxides, (X-6) crosslinking aid include (X-7) other components.
[0185]
((X-1) organic peroxide)
as the (X-1) an organic peroxide, it can be used any suitably organic peroxides that can act as an olefin-based rubber crosslinking agent.
[0186]
(X-1) Specific examples of the organic peroxide, dicumyl peroxide, di -tert- butyl peroxide, 2,5-di - (tert-butylperoxy) hexane, 2,5-dimethyl-2,5 - di - (tert- butylperoxy) hexane, 2,5-dimethyl-2,5-di - (tert- butylperoxy) hexyne-3,1,3-bis (tert- butylperoxy-isopropyl) benzene, 1,1 - bis (tert- butylperoxy) -3,3,5-trimethylcyclohexane, n- butyl-4,4-bis (tert- butylperoxy) valerate, benzoyl peroxide, p- chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert- butyl peroxybenzoate, tert- butylperoxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.
[0187]
(X-1) organic peroxides, can either be used alone, it may be used in combination of two or more thereof.
(X-1) organic peroxide of the olefinic rubber 100 parts by weight, 0.1 to 5 parts by weight, preferably from 0.5 to 5 parts by weight, more preferably 0.5 to 4 parts by weight used in the range is desirable. If the amount of (X-1) organic peroxide is within the above range, less bloom to the surface of the crosslinked molded article is preferable to indicate the crosslinking properties of rubber molding is excellent.
[0188]
((X-2) carbon
black) as the (X-2) carbon black, SRF, GPF, FEF, MAF , HAF, ISAF, SAF, FT, various carbon blacks such as MT; silane coupling these carbon black and surface-treated carbon black surface-treated with such agents.
[0189]
(X-2) The amount of carbon black, of the olefinic rubber 100 parts by weight, 10 to 300 parts by weight, preferably 10 to 200 parts by weight, more preferably from 10 to 100 parts by weight of about .
If contain (X-2) carbon black within the above range, the mechanical properties such as tensile strength and abrasion resistance can be obtained a laminate which has been improved, impairing other physical properties of the laminate It preferable since no can increase the hardness.
[0190]
((X-3) Antioxidant)
When (X-3) containing an antioxidant, it is possible to prolong the product life of the compact.
The (X-3) Antioxidant, conventional antioxidants, such as amine-based antiaging agent, a phenol-based antioxidant, can be used sulfur-based anti-aging agents.
[0191]
The (X-3) anti-aging agent, specifically, a phenyl butyl amine, N, N-di-2-naphthyl -p- phenylenediamine, 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine ( Also known as: 4,4'-dicumyl-diphenylamine) aromatic secondary amine-based anti-aging agents such as, 2,2,4-trimethyl-1,2-dihydroquinoline polymer and the like of the amine-based antioxidant, dibutylhydroxytoluene toluene, tetrakis [methylene (3,5-di -t- butyl-4-hydroxy) hydro-cinnamate] phenol antioxidant such as methane, bis [2-methyl-4- (3-n-alkylthio propionyloxy) -5-t-butylphenyl] thioether antioxidants such as sulfides; dibutyldithiocarbamate such dithiocarbamate nickel System antioxidant; 2-mercapto-benzoyl imidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, sulfur-based antioxidant such as distearyl thiodipropionate and the like.
[0192]
These (X-3) anti-aging agents, can either be used alone, it may be used in combination of two or more thereof.
The amount of (X-3) antioxidant, of the olefinic rubber 100 parts by weight from 0.5 to 5.0 parts by weight, preferably 0.5 to 4.5 mass parts, more preferably 0. 5 to 4.0 mass parts. Within the above range, the laminate is preferable because it is excellent in heat aging resistance.
[0193]
((X-4) softener)
The (X-4) softeners can be used conventional rubber softener is blended in, widely components known as processing aids and the like.
Specifically,
paraffinic process oil, naphthenic process oil, petroleum-based softening agent such as aromatic process oils;
synthetic oil-based softening agent;
ethylene and α- olefin co-oligomer;
paraffin waxes;
liquid paraffin;
white oil (white oil);
petrolatum;
coal tar, coal tar-based softeners such as coal tar pitch;
castor oil, Nishikimiyu, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, peanut oil, Japan wax, rosin, pine oil, dipentene, pine tar, vegetable oil softening agents tall oil;
black sub, white sub, sub candy sub etc. (factice);
beeswax, carnauba wax, wax and lanolin;
ricinoleic acid, palmitic acid , stearic acid, linoleic acid, lauric acid, myristic acid, barium stearate, calcium stearate Arm, magnesium stearate, zinc stearate, fatty acids such as zinc laurate, fatty acid salts and esters;
dioctyl phthalate, dioctyl adipate, ester plasticizers such as dioctyl sebacate;
coumarone-indene resin;
Phenol formaldehyde resins;
terpene phenol resins;
polyterpene resins;
synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic-alicyclic petroleum resins, aliphatic family-aromatic petroleum resins, hydrogenated modified alicyclic hydrocarbon resins, hydrogenated hydrocarbon resins, liquid polybutene, liquid polybutadiene, and petroleum hydrocarbon resins such as atactic polypropylene.
[0194]
Fatty Among them, petroleum softeners, phenol-formaldehyde resins, are preferred petroleum hydrocarbon resins, fatty acids, petroleum-based softening agent, more preferably petroleum hydrocarbon resins, fatty acids, petroleum-based softening agent is particularly preferred.
[0195]
Among the petroleum softening agent is preferably petroleum process oil, paraffinic process oil Among them, naphthenic process oil, more preferably such aromatic process oils, paraffin-based process oil is particularly preferred. Also in the petroleum hydrocarbon resin, aliphatic cyclic hydrocarbon resins are preferred. Paraffinic process oil Among these softening agents is particularly preferred.
These softeners can either be used alone, it may be used in combination of two or more thereof.
[0196]
The amount of (X-4) softening agents include, but are not limited to a particular of the olefinic rubber 100 parts by weight, an amount of usually less than 200 parts by weight, preferably from 0 to 100 parts by weight, more preferably 0 to 80 parts by mass, more preferably from 0 to 70 parts by weight, particularly preferably from 0 to 60 parts by weight.
[0197]
(X-5) a metal oxide
as the metal oxide, can be selected appropriately according to the application of the laminate, it can be used as a mixture of two or more kinds in combination. Zinc white (for example, META-Z102) Specific examples of the metal oxide (trade name: zinc oxide, such as Inoue Lime Industry Co., Ltd.), and magnesium oxide. Its amount is normally of the olefinic rubber 100 parts by weight, usually 0.5 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, more preferably 0 a .5 to 5 parts by weight.
[0198]
((X-6) coagent)
The (X-6) crosslinking aids include sulfur; quinone dioxime compounds such as p- quinone dioxime; polyfunctional monomers such as trimethylolpropane triacrylate, polyethylene glycol such as dimethacrylate (meth) acrylate compound; diallyl phthalate, allyl compounds such as triallyl cyanurate; m-phenylene bismaleimide maleimide compound of; and divinylbenzene. (X-6) coagent may be used alone, it may be used in combination of two or more.
[0199]
The amount of (X-6) coagent, especially but not limited to, of the olefinic rubber 100 parts by weight, usually 0 to 4.0 mass parts, preferably 0 to 3.5 mass parts , more preferably 0 to 3.0 parts by mass, more preferably 0.1 to 3.0 parts by mass. The amount of (X-6) coagent, (X-1) preferably 0.5 to 2 mol of the organic peroxide to 1 mol, even more preferably at an amount of approximately equimolar desirable.
[0200]
((X-7) Other Components)
The (X-7) Other components additives, fillers, foaming agents, antioxidants, processing aids, surfactants, etc. weathering agent, a conventionally rubber composition It includes various additive components to be. It may also optionally contain a resin component other than the olefin rubber.
[0201]
The filler, silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine powder talc, talc, fine powder silicic acid, and inorganic fillers such as clay. These fillers, 0-300 parts by weight of the olefinic rubber 100 parts by weight, preferably to 0 to 200 parts by weight approximately. By using fillers, the tensile strength, it is possible to obtain a laminate mechanical properties are improved, such as tear strength and abrasion resistance, it is possible to increase the hardness without deteriorating other properties of the laminate .
[0202]
The resin composition according to the present invention, from the viewpoint of long the material life, it also preferably contains an antioxidant. As the antioxidant,
phenylnaphthylamine, 4,4 '- (α, α- dimethylbenzyl) diphenylamine, N, aromatic secondary amine-based stabilizers such as N'- di-2-naphthyl -p- phenylenediamine;
2,6-di -t- butyl-4-methylphenol, tetrakis - [methylene-3- (3 ', 5'-di -t- butyl-4'-hydroxyphenyl) propionate] phenolic stabilizers such as methane ;
; benzimidazole-based stabilizer 2-mercaptobenzimidazole and the like; bis [2-methyl -4- (3-n- alkylthio propionyloxy) -5-t-butylphenyl] thioether stabilizer sulfides
dibutyldithiocarbamate dithiocarbamate stabilizers such as nickel;
quinoline stabilizer polymer such as 2,2,4-trimethyl-1,2-dihydroquinoline
, and the like. These may be used alone or in combination of two or more.
[0203]
Antioxidants, of the olefinic rubber 100 parts by weight, for example 5 parts by weight or less, preferably in an amount of 3 parts by mass or less.
Also the olefinic rubber, the various additives may be incorporated into known rubber composition may contain as necessary.
[0204]
The olefin-based rubber may be blended with surfactant. As the surfactant, di -n- butylamine, dicyclohexylamine, mono- gills alkanolamine, triethanolamine, "Akuchingu B (Yoshitomi Pharmaceutical Co., Ltd.), amines such as" Akuchingu SL (Yoshitomi Pharmaceutical Co., Ltd.), polyethylene glycol, diethylene glycol, polyethylene glycol, lecithin, thoria reroute trimellitate, aliphatic and zinc compound of an aromatic carboxylic acid (eg, "Struktol Activator 73", "Struktol IB 531", manufactured by "Struktol FA541" Schill & Seilacher Co.), "ZEONET ZP "(Nippon Zeon Co., Ltd.), octadecyl trimethyl ammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds (e.g.," lipo card 2HT F "(Lion Specialty Lee Chemicals Co., dialkyl chloride (C14-18) dimethyl ammonium) As. Surfactants, and the like, lipoic card 2HTF is most preferred.
[0205]
The olefin-based rubber, when formulating a surfactant, the amount of surfactant is of the olefinic rubber 100 parts by weight, for example 0.2 to 10 parts by weight, preferably 0.3 to 8 wt parts, more preferably 0.3 to 7 parts by mass, particularly preferably 0.5 to 7 parts by mass, and most preferably 1 to 6 parts by mass. Surfactants can be appropriately selected according to the application, it can be used as a mixture of two or more kinds in combination.
[0206]
The olefin-based rubber may be blended with pseudo gel inhibitor. The pseudo gel inhibitor, for example, "NHM-007" (manufactured by Mitsui Chemicals, Inc.).
The olefin-based rubber, when formulating a pseudo gel inhibitor, the amount of the pseudo-gel inhibitor, of the olefinic rubber 100 parts by weight, usually from 0.1 to 15 parts by weight, preferably 0.5 to 12 parts by weight, more preferably 1.0 to 10 parts by weight.
[0207]
The olefin-based rubber further other additives if necessary may be blended. Other additives, heat stabilizers, weathering stabilizers, antistatic agents, coloring agents, lubricants and a thickener.
[0208]
The olefin-based rubber may be blended as necessary other resin components other than the olefin rubber. Other resin components, but are not particularly limited, and a polyolefin resin.
[0209]
An olefin rubber and blending the polyolefin resin, it is possible to adjust the product hardness, it is possible to reduce the compound viscosity at the processing temperature, it is possible to improve the workability. Also it is handled as a thermoplastic elastomer, handling properties, preferably the width of the kneading technique spreads.
[0210]
As the polyolefin resin, usually, the number average molecular weight of standard polystyrene as measured by GPC is 10,000 or more polyolefin resin is preferably used.
As the polyolefin resin, alpha-olefin homopolymers, alpha-olefin copolymer. The alpha-olefin homopolymers, polyethylene, polypropylene and the like, and the alpha-olefin copolymers, alpha-olefin interpolymers of ethylene-C3-20 thereof. The α- olefin copolymer ethylene-C3-20, ethylene-propylene rubber (EPR), propylene-ethylene rubber (PER), ethylene-Butenraba (EBR), ethylene Okutenraba (EOR) and the like and the like.
[0211]
As the polyolefin resin, Among these, polyethylene, ethylene · alpha-olefin copolymer, polypropylene is preferred.
Incidentally, the polyolefin resin may be used alone or may be used two or more kinds.
[0212]
The case of blending a polyolefin resin in an olefin-based rubber, the content of the polyolefin resin, of the olefinic rubber 100 parts by weight, for example, 1 to 100 parts by weight, preferably 5 to 80 parts by mass, more preferably from 10 to 50 is parts by weight approximately.
[0213]
Within the above range, it is possible to adjust the hardness of the laminate, it is possible to reduce the compound viscosity at the processing temperature, it is possible to improve the workability. Also it is handled as a thermoplastic elastomer, handling properties, preferably the width of the kneading technique spreads.
[0214]
layers constituting the laminate of the present invention (B), the adhesive resin layer, i.e., a layer formed from the above adhesive resin.
[0215]
Layer (B) has only to be made using at least an adhesive resin, but not necessarily preclude further contain other components as long as they do not impair the adhesive properties, generally, made using only the adhesive resin that is a layer.
[0216]
layers constituting the laminate of the present invention (C) is a layer comprising a rubber containing a Group 15 element described above.
[0217]
Layer (C) has only to be made using a rubber containing at least a Group 15 element, but usually not only rubber containing a Group 15 element, with the other components as a starting material, a layer to be produced. Layer (C) is usually a layer made by using a rubber containing a Group 15 element, crosslinked. As a component other than the rubber containing the Group 15 element, e.g., (X-1 ') sulfur, as well as described in the description of the layer (A) (X-2) carbon black, (X-3) antioxidant, (X-4) softener, (X-5) a metal oxide, (X-6) crosslinking aid include (X-7) other components. (X-2) type and amount of ~ (X-7) is described in the description of the layer (A) (X-2) can be ~ and (X-7) with those similar respectively.
[0218]
((X-1 ') sulfur)
as a layer crosslinking agent in forming the (C), described in the description of the layer (A) (X-1) preclude necessarily the use of organic peroxides no. in particular, if the nitrile rubber is used as rubber containing a group 15 element, sulfur is preferably used rather as a cross-linking agent.
[0219]
(X-1 ') sulfur, based on 100 parts by mass of the rubber containing the Group 15 element, desirably used at 0.5 to 5.0 parts by weight. (X-1 ') When the amount of sulfur is in the above range is preferable because good vulcanizate properties can be obtained.
[0220]
Here, if the (X-1 ') sulfur is used as the crosslinking agent, as (X-6) coagent, guanidine-based vulcanization accelerator such as diphenyl guanidine, thiuram vulcanization accelerator such as tetramethylthiuram disulfide agents, dithiocarbamate based vulcanization accelerator, 2-thiazole vulcanization accelerators such as mercaptobenzothiazole, and, N-t-butyl-2-benzothiazole sulfenamide sulfenamide vulcanization accelerators such as It is preferably used. If (X-6) using these vulcanization accelerators as a crosslinking agent, relative to 100 parts by mass of the rubber containing the Group 15 element, (X-6) coagents, 0.5-5. It is desirably used in 0 part by weight.
[0221]
Incidentally, as the crosslinking agent, as described in the description of the layer (A) when (X-1) organic peroxide can be used, the type and amount of (X-6) coagent, wherein It may be as described in the description of the layer (a) (X-6), respectively a crosslinking aid as well.
[0222]
On the other hand, (X-2) carbon black, (X-3) Antioxidant, (X-4) softener, (X-5) a metal oxide, (X-7) the type and amount of other components, described in the description of the layer (a) (X-2) carbon black, (X-3) antioxidant, (X-4) softener, (X-5) a metal oxide, (X-7) it can be made for each and other components as well.
[0223]
(Preparation method of the material constituting the layers)
is not particularly limited in a process of preparing the materials constituting the layers. The material constituting the layer (A) is, if only the olefinic rubber, the material constituting the layer (C), when only rubber containing a Group 15 element, it uses each rubber described above can do. As for the layer (B), it is possible to accept the above-mentioned adhesive resin.
[0224]
Materials constituting each layer, if it contains components other than the rubber described above, i.e., when the layer (A) is made of a resin composition containing an olefin-based rubber, the layer (C) is incorporated with Group 15 element If made of a resin composition comprising a rubber, for example, it may be prepared in the following manner.
[0225]
The resin composition, rubber (olefin rubber (layer (A)), rubber containing a Group 15 element (layer (C)), (X-1) an organic peroxide or (X-1 ') Sulfur , (X-2) carbon black, (X-3) antioxidant, (X-4) softener, (X-5) a metal oxide, (X-6) coagent, and (X-7) among such other components, it can be prepared by appropriately blending the ingredients used for forming each layer.
[0226]
Method for preparing the resin composition is not particularly limited, for example, the respective components contained in the resin composition, for example, a mixer, kneader, kneader, known conventional roll or the like, of the twin-screw extruder a method of mixing using a continuous mixer such as, the solution was prepared in which each component is dissolved or dispersed in the resin composition, methods and the like to remove the solvent.
[0227]
(Laminate)
The laminate of the invention, as described above,
olefin-based rubber layer (A),
the adhesive resin layer (B),
a layer (C) comprising a rubber containing a Group 15 element
is the including a structure formed by laminating in the order.
[0228]
The thickness of each layer constituting the laminate is not particularly limited, the layer (A) is usually a 0.1 mm ~ 10.0 mm, preferably 0.5 mm ~ 5.0 mm, the layer ( B) is usually a 0.01 mm ~ 2.0 mm, preferably 0.05 mm ~ 0.5 mm, the layer (C) is usually a 0.1 mm ~ 10.0 mm, preferably 0. it is a 5mm ~ 5.0mm. The thickness of the laminate as a whole is not particularly limited, usually from 1.0 mm ~ 20.0 mm, preferably 2.0 mm ~ 10.0 mm.
[0229]
As the laminate are bonded via the layer (A) and the layer (C) Togaso (B), have a layer configuration of layer (A) / layer (B) / layer (C) may be Re, it is not particularly limited as the layer structure of the laminate as a whole.
[0230]
(Method for producing a laminate)
As a method for producing the laminate of the present invention is not particularly limited, a method can be mentioned to obtain a laminate, for example by the following method (a). Incidentally, the method (a), after obtaining the layered product, it may be subjected to cross-linking step, or perform secondary vulcanization process in the primary vulcanization, etc. in an oven, lamination with a layer comprising a crosslinked rubber body may be obtained.
[0231]
(A) layer of material which constitutes the (A), a kneader, a roll, a Banbury mixer, kneaded by a mixer such as a inter mixer, forming a layer (A) by extruding by an extruder, a layer of (C) the material constituting, kneader, roll, Banbury mixer, kneaded by a mixer such as a inter mixer, extruder layer (C) formed by extrusion by a layer (a) and a layer (C), the layer by adhering by (B), the layer (a) layer and (C), but a method of obtaining a laminate in contact via a layer (B).
[0232]
Incidentally, in the production of the laminate, the layer (A) and the layer (C) Togaso the laminate in contact via a (B), be pressed forming layer (A) and the layer (C) from the viewpoint of increasing the peel strength between.
[0233]
(Cross-linking step, primary curing)
The crosslinked process or primary vulcanization, the layer (A), in advance by blending components necessary for crosslinking, such as pre-cross-linking agent to the material constituting the layer (C), step out the crosslinking by heating (e.g., 150 ~ 240 ℃), electron beam (e.g., electron rays having energy of 0.1 ~ 10 MeV), include the step of performing crosslinking by irradiating the laminate. The irradiation of the electron beam, the absorbed dose of the laminate, is usually 0.5 ~ 36Mrad, preferably 0.5 ~ 20 Mrad, and more preferably carried out so that the 1 ~ 10 Mrad.
[0234]
Incidentally, in the crosslinking step or the primary vulcanization, when performing crosslinking by heating, applying heat while press molding is preferable from the viewpoint of increasing the peel strength between the layer (A) and the layer (C) .
[0235]
(2 vulcanization)
2 vulcanization is a process performed after the primary vulcanization, by performing heating (e.g. 0.99 ~ 200 ° C.), the step to sufficiently promote vulcanization (crosslinking) is there.
[0236]
The laminate of the invention, it is possible to satisfy the various properties required by the layer structure can be used for various applications.
[0237]
The laminate of the present invention can be used in a variety of applications. The laminate of the present invention can be used for example for the automotive, motorcycle, industrial machinery, as a construction machinery or members of agricultural machines. Specific examples of the member, industrial roll, packing (for example, condenser packings), gaskets, belts (e.g., thermal insulation belt, copier belts, conveyor belts), hoses, such as automotive hoses (e.g., turbocharger hose, water hose, brake reservoir hose, radiator hose, air hose), rubber vibration isolators, vibration-proof material or damping material (for example, engine mount, motor mount), muffler hanger, cable (ignition cables, flexible cable, high-tension cable ), wire covering material (high-voltage wire covering material, a low-voltage electric wire covering material, marine wire covering material), glass run channels, color skin material, paper feed rolls, roofing sheet, and the like.
[0238]
Further, olefin rubbers such as ethylene-alpha-olefin-nonconjugated polyene copolymer is excellent in moldability and crosslinking properties, it is possible to obtain a heat stability superior crosslinked product, having a layer (1) by the laminate can be suitably used for applications expected to be long-term use at high temperatures. Olefin-based rubber, if it is the ethylene · alpha-olefin · VNB copolymer, especially since the excellent fatigue resistance, over a long period of time, preferably for to withstand use under severe conditions.
[0239]
Among these, the laminate of the present invention is suitably used in applications requiring the in automotive exterior parts and heat resistance. Applications of the laminate, for example, a laminate of the present invention include a hose having at least as a part. The hose, but not limited to their use for the automotive, motorcycle, industrial machinery, it is preferable to use any of the applications for construction equipment or agricultural machinery.
Hose of the present invention, the laminate of the present invention may have at least in part, may be a hose which is formed of only the laminate of the present invention.
Example
[0240]
It will be described in further detail following shows an example for the present invention, but the invention is not limited thereto.
(Measurement and evaluation methods)
following production examples, examples and comparative examples, measurement and evaluation method of each characteristic is as follows.
[0241]
(Composition of the ethylene-alpha-olefin-nonconjugated polyene copolymer, and B values)
of the ethylene-alpha-olefin-nonconjugated polyene copolymer, the mass fraction of each constituent unit (% by weight) and B value, 13 were determined by measurement by C-NMR. Measurements using ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL), measurement temperature: 120 ° C., measurement solvent: o-dichlorobenzene / deuterated benzene = 4/1, the number of integrations: at 8000 times, co polymer 13 spectra C-NMR obtained by measuring.
[0242]
(Iodine value)
iodine value of the ethylene-alpha-olefin-nonconjugated polyene copolymer was determined by titration. Specifically, it was measured by the following method.
[0243]
Ethylene-alpha-olefin-nonconjugated polyene copolymer 0.5g was dissolved in carbon tetrachloride 60 ml, was added a small amount of Wiesbaden reagent and 20% potassium iodide solution, titrated with 0.1 mol / L sodium thiosulfate solution did. Starch indicator was added in the vicinity of the end point, titrated until well where stirring heliotrope disappears was calculated g number of iodine as the amount of halogen to be consumed for the sample 100 g.
[0244]
(Intrinsic viscosity [eta])
The intrinsic viscosity of the ethylene-alpha-olefin-nonconjugated polyene copolymer [η] (dl / g), using Ltd. Rigo Co. fully automatic intrinsic viscometer, temperature: 135 ℃, measurement solvent: was measured in decalin.
[0245]
(Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn))
weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), gel permeation chromatography is a numerical value in terms of polystyrene as measured by chromatography (GPC). Measurement apparatus and conditions are as follows. Further, the molecular weight, to prepare a calibration curve using commercially available monodisperse polystyrene was calculated on the basis of the conversion method.
Apparatus: Gel permeation chromatograph Alliance GP2000 (manufactured by Waters),
analyzer: Empower (manufactured by Waters),
column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (7.5mmI.D. × 30cm, Tosoh Corporation Ltd.),
column temperature: 140 ° C.,
mobile phase: o-dichlorobenzene (0.025% BHT content),
detector: differential refractometer (RI), flow rate: 1.0 mL / min,
injection volume: 400 [mu] L,
sampling time interval: 1s,
column calibration: monodisperse polystyrene (Tosoh Corporation),
the molecular weight in terms of: calibration method considering former law EPR conversion / viscosity.
[0246]
(Complex viscosity eta * )
as a rheometer, using a viscoelasticity measuring apparatus Ares (Rheometric Scientific Inc.), 190 ° C., at a strain of 1.0% of the conditions, the complex viscosity at a frequency = 0.01 rad omega / s eta * ( omega = 0.01) , the frequency omega = 0.1 rad / s complex viscosity at eta * ( omega = 0.1) , the frequency omega = complex viscosity at 10 rad / s eta * ( omega = 10) and the frequency omega = 100 rad / s the complex viscosity η at * ( Omega = 100) (both units of Pa · sec) was measured. Further, from the results obtained eta * ( omega = 0.1) and eta * ( omega = 100) ratio of the complex viscosity of the (eta * ratio) at a P value (eta * ( Omega = 0.1) / Ita * ( Omega = 100) ) was calculated.
(1000 long chain branches per carbon atoms (LCB 1000c ))
was measured by the above requirement (V-i) method described above in section ~ (V-iii).
[0247]
(1) Mooney viscosity (ML (1 + 4) 100 °
C.) Mooney viscosity at 100 ℃ (ML (1 + 4 ) 100 ℃) is in compliance with JIS K6300, a Mooney viscometer ((Co. ) using a Shimadzu SMV202 type) was measured under the conditions of 100 ° C..
[0248]
(2) vulcanization induction time
using a rubber blend of uncrosslinked in Examples and Comparative Examples, vulcanization measuring device: by MDR 2000 (ALPHA TECHNOLOGIES Co.), measurement conditions of temperature 160 ° C. and for a time of 30 minutes, induction time (TS1), was measured as follows.
[0249]
The torque variation obtained under the conditions of constant temperature and constant shear rate was measured. The time from the minimum torque value to go up torque 1 point (1 dNm) vulcanization induction time; was (TS1 minute).
[0250]
(3) curing rate
by using a rubber composition of the uncrosslinked in Examples and Comparative Examples, the measurement device: a MDR 2000 (ALPHA TECHNOLOGIES Co.), measurement conditions of temperature 160 ° C. and for a time of 30 minutes, the vulcanization rate the (TC90) was measured as follows.
[0251]
The torque variation obtained under the conditions of constant temperature and constant shear rate was measured. The time to achieve 90% of the torque of the difference between the maximum value and the minimum value of the torque vulcanization rate; was (TC90 min).
[0252]
(T-peel test)
The peeling strength of the laminate was measured by the following method.
Example, a laminate obtained in Comparative Example, in compliance with JIS K6854-3, measurement temperature: 23.0 ° C., test speed: 200.0mm / min, specimen width: T-type peeling at 25.0mm test was performed to measure the peel strength.
[0253]
(Surface Swelling Test)
The surface swelling test of the laminate was carried out in the manner described below.
Example, a crosslinked rubber sheet having a thickness of 5mm obtained in Comparative Example (laminate), cut into 8 cm × 8 cm square, to obtain a laminated body for measurement.
[0254]
On the layer B of the laminate for measurement were prepared bank circular silicone sealant. 該土 hand, the diameter of the interior of the bank is the 5 cm, so that the height of about 2 cm, was produced on the layer B.
[0255]
In the interior of the bank, the lubricating oil (Nippon Sun Oil, Ltd., IRM903) poured 2.4g.
And held at a temperature 80 ° C., to observe the surface state every hour.
From the surface of the lubricating oil, × a case where the surface of the laminate protruding appeared a rubber swelling of laminate (swelling), from the surface of the lubricating oil, without ○ (swelling the case where the surface of the laminate did not appear ) as it was assessed by visual inspection.
[0256]
(Modulus, tensile stress at break, tensile elongation at break)
modulus of the sheet, the tensile stress at break, tensile elongation at break was measured by the following method.
The JIS K 6251 3 No. dumbbell specimen as described in (1993) was prepared by punching a sheet, according to the method prescribed in JIS K6251 third term by using this test specimen, measurement temperature 25 ° C., tensile subjected to tensile test at a rate of 500 mm / min condition, the tensile stress (100% modulus (M100)) when elongation is 100% tensile stress (200% modulus (M200 when elongation is 200% )), tensile stress (300% modulus (M300 when elongation is 300%)), tensile stress at break (TB) and tensile elongation at break (EB) were measured.
[0257]
(Hardness test (Shore -A
hardness)) in accordance with JIS K 6253, the measurement of the sheet hardness (type A durometer, HA), using a sheet-like rubber molded article six 2mm to have a smooth surface, flat It was carried out with a thickness of about 12mm by stacking portion. However, those foreign substances on the test piece, some of the air bubbles, and some of the flaws were not used. Further, the dimensions of the measurement surface of the specimen was sized to indentor tip can be measured at a distance above 12mm from the edge of the specimen.
[0258]
(Heat aging resistance
test) in accordance with JIS K 6257, was subjected to a heat resistance aging test. That is, after aged placed 168 hours sheet during 180 ° C. oven, measuring temperature 23 ° C., subjected to tensile test at a tensile rate of 500 mm / min condition, tensile stress at break (TB) and tensile elongation at break ( EB) were measured. Further, in terms similar to the method (hardness test (Shore -A hardness)), the hardness was measured.
[0259]
(Flexural fatigue resistance)
conforming to JIS K6260, using a groove-free specimen by De Mattia flexing test machine, to evaluate the resistance to crack initiation and crack growth when given repeated bending test piece.
Measurement temperature was 23 ° C., and records the number of times when the specimen is cut.
In the case where even give 500,000 times bending was not cut specimens, where the test was terminated, to confirm the status of the test piece was visually.
[0260]
[Production Example 1]
(Production of ethylene-propylene-VNB copolymer (A-1))
by using a polymerization vessel volume 300L equipped with a stirring blade, continuous, ethylene, propylene, 5-vinyl-2 polymerization reaction of norbornene (VNB) was carried out at the 87 ℃.
[0261]
Hexane (feed rate: 32.6L / h) is as a polymerization solvent by using, sequentially, the ethylene feed rate is 3.6 kg / h, propylene amount is 6.1 kg / h, VNB feed rate is 290 g / h and as the hydrogen feed rate is 6.3NL / h, it was continuously fed to the polymerization reactor.
[0262]
The polymerization pressure 1.6MPaG, while maintaining the polymerization temperature at 87 ° C., with di (p- tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as a main catalyst, feed rate so as to be 0.0015 mmol / h, it was continuously fed to the polymerization vessel. Further, as co-catalysts (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) The feed rate 0.0075 mmol / h, triisobutylaluminum (TIBA) the feed rate 20 mmol / h as the organoaluminum compound and so that, were continuously fed to each polymerization reactor.
[0263]
Thus, ethylene, propylene and ethylene-propylene-VNB copolymer formed from VNB is a solution containing 15.2 wt% was obtained. Polymerization reactor was added a small amount of methanol to the polymerization reaction solution was withdrawn from the bottom the polymerization reaction was stopped, after separation of the ethylene-propylene-VNB copolymer in the steam stripping from the solvent, under reduced pressure overnight at 80 ° C. dry.
[0264]
By the above operation, ethylene, propylene and ethylene-propylene-VNB copolymer formed from VNB polymer (A-1) was obtained at a rate per hour 4.7 kg.
The obtained copolymer physical properties of (A-1) was measured by the aforementioned methods. The results are shown in Table 1. Here, the term in Table 1 "VNB-IV" refers to an iodine value based on the VNB.
Incidentally, the obtained copolymer (A-1), also referred to as "VNB-EPT".
[0265]
[Table 1]
[0266]
Production Example 2A]
(ethylene-vinyl acetate copolymer)
by Du Pont-Mitsui Poly Chemical Co. EV150 (MFR (190 ℃, 2.16kg load) = 30 g / 10 min, density = 960 kg / m 3 , vinyl acetate content = 33 mass%, the melting point (DSC) = 61 ℃), was used as the ethylene-vinyl acetate copolymer.
[0267]
The ethylene-vinyl acetate copolymer, after 4 minutes pressing at 160 ° C. using 50 ton press molding machine, and pressed for 2 minutes at room temperature, thickness 250 [mu] m, 15cm square film (hereinafter, "EVA film") prepared did.
[0268]
Using this, it was adhesion evaluation.
In the following description, the ethylene-vinyl acetate copolymer, is referred to as "EVA".
[0269]
Production Example 2B]
(silane-modified ethylene production of vinyl acetate copolymer)
Ethylene-vinyl acetate copolymer (manufactured by Mitsui-DuPont Polychemicals made EV260: MFR (190 ℃, 2.16kg load) = 6 g / 10 min, density = 950 kg / m 3 , vinyl acetate content = 28 wt%, the melting point (DSC) = 72 ℃) 100 parts by mass,
1.7 parts by weight of vinyltrimethoxysilane as a silane compound,
dicumyl peroxide as a free radical generator 0.15 parts by weight, and,
dodecyl mercaptan 0.03 parts by weight as a reaction inhibitor
was extruded with a formulation consisting in supplying the multi-screw extruder 65mmφ kneaded at a resin temperature of 200 ° C. or higher, cooling pellets to obtain a silane-modified ethylene-vinyl acetate copolymer turned into.
[0270]
The silane-modified ethylene-vinyl acetate copolymer, after 4 minutes pressing at 160 ° C. using 50 ton press molding machine, and pressed for 2 minutes at room temperature, thickness 50 [mu] m, 15cm square film (hereinafter, "SMEVA film") It was prepared.
[0271]
Using this, it was adhesion evaluation.
In the following description, the resulting silane-modified ethylene-vinyl acetate copolymer, is referred to as a "SMEVA".
Examples and Comparative Examples, the copolymer (A-1), in addition to the EVA and the SMEVA, were used the following commercially available products.
[0272]
(Ethylene-alpha-olefin-nonconjugated polyene copolymer)
Mitsui EPT 2060M: Ethylene-propylene-ENB copolymer, ML (1 + 4) 125 ℃ (ASTM D 1646) of 40, an ethylene content (ASTM D 3900) is 55wt %, indicating ENB content (ASTM D 6047) is 2.3 wt%, manufactured by Mitsui Chemicals Co., Ltd. Mitsui EPT properties of 2060M Table 2.
In addition, Mitsui EPT 2060M, also referred to as "ENB-EPT."
[0273]
[Table 2]
[0274]
(Nitrile
rubber) Nipol1042: nitrile-butadiene rubber, manufactured by Nippon Zeon Co., Ltd.
It is to be noted, also referred to as "NBR" the Nipol1042.
[0275]
[Example
1-1] (Preparation of a composition comprising a VNB-EPT)
As a first step, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), 100 parts by weight of 30 seconds containing the VNB-EPT of kneaded, and then to this, 30 parts by weight of FEF carbon (Asahi 60G: manufactured by Asahi carbon Co., Ltd.), 45 parts by weight of SRF carbon (Asahi 50G: manufactured by Asahi carbon Co., Ltd.), 40 parts by mass FT carbon (Asahi thermal: Asahi carbon Co., Ltd.), magnesium oxide 5 parts by weight (Mag 150: manufactured by Kyowa chemical industry Co., Ltd.), 1 part by weight of camellia stearate (beads stearic acid: manufactured by NOF Corporation), 4 parts by weight of 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine (Nocrac CD, Ouchi Shinko Kagaku Co.), 47 parts by weight of process oil (Diana process PS430: manufactured by Idemitsu Kosan Co., Ltd.), Contact Beauty 3 parts by weight of trimethylolpropane trimethacrylate (High Cross M: Seiko Chemical Co., Ltd.), and the mixture was kneaded for 2 minutes at 140 ° C.. Thereafter, performs cleaning to increase the ram, further, subjected to 1 minute kneading, discharged at about 0.99 ° C., to obtain a first phase of the formulation.
[0276]
Next, as a second step, the blend obtained in the first stage, 8 Inchiro - Le (Nippon Roll Co., Ltd., before the surface temperature 50 ° C. of the roll, the surface temperature of 50 ° C. of the rear roll, front roll wound rotational speed 16 rpm, the rotational speed 18 rpm) of the rear roll, this, 3 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B: manufactured by NOF Corporation ) and kneaded for 10 minutes was added to obtain a non-crosslinked resin composition (rubber compound) (a composition comprising a VNB-EPT).
[0277]
(Preparation of a composition comprising a NBR)
as a first step, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), the NBR of 100 parts by weight kneaded for 30 seconds element, then to this, 40 parts by weight FEF carbon (Asahi 60G: manufactured by Asahi carbon Co., Ltd.), magnesium oxide 5 parts by weight (Mag 150: manufactured by Kyowa chemical industry Co., Ltd.), 1 part by weight of stearic acid (beads stearic acid Tsubaki, manufactured by NOF Corp.), 2 parts by weight of 2-mercaptobenzimidazole (Nocrac MB: manufactured by Ouchi Shinko Co., Ltd.), pentaerythritol tetrakis 1 part by weight {3- (3'-5-di -tert- butyl-4'-hydroxyphenyl) propionate} (1010 : BASF Corporation), and the mixture was kneaded for 2 minutes at 140 ° C.. Thereafter, performs cleaning to increase the ram, further, subjected to 1 minute kneading, discharged at about 0.99 ° C., to obtain a first phase of the formulation.
[0278]
Next, as a second step, the blend obtained in the first stage, 8 Inchiro - Le (Nippon Roll Co., Ltd., before the surface temperature 50 ° C. of the roll, the surface temperature of 50 ° C. of the rear roll, front roll speed 16 rpm, wrapped around the rotary speed 18 rpm) of the rear roll, 0.7 parts by weight of N-tert-butyl-2-benzothiazolyl sulfenamide (NS: manufactured by Ouchi Shinko Co., Ltd.) and 1.5 parts by mass and kneaded for 10 minutes was added sulfur parts to obtain uncrosslinked resin composition (rubber compound) (a composition comprising a NBR).
[0279]
(Preparation of the laminate, evaluation)
(T-peel preparation of laminates for testing)
and the respective compositions comprising a VNB-EPT and compositions comprising NBR out the partial sheet. Then divided out unvulcanized rubber sheet (sheet of a composition comprising a sheet and NBR composition comprising a VNB-EPT) 50 g, were each sandwiched up and down individually Lumirror (oriented polyester (polyethylene terephthalate) film) . Each unvulcanized rubber sheet vertically is sandwiched by Lumirror 50 ton with a press molding machine, the sheet is 2 minutes at 120 ° C. of a composition comprising a VNB-EPT, the sheet of a composition comprising a NBR is 80 ° C. in 2 minutes, respectively pressed, t (thickness) = 1 mm, length and width are both fabricated 20cm unvulcanized rubber sheet, respectively.
[0280]
Then, the unvulcanized rubber sheet obtained from the composition containing the VNB-EPT after pressing has been performed (A layer), the EVA film (B layer), and, after the press has been performed the unvulcanized rubber sheet obtained from a composition comprising NBR (C layer), was cut into this press dimensions which each (length 15cm × width 15cm × thickness 1 mm). Peeling the upper and lower Lumirror after cutting, then superimposed and unvulcanized rubber sheet A layer, the EVA film of B layer, the unvulcanized rubber sheet C layer in this order. When overlaying the portion of the unvulcanized rubber sheet: (width 5 cm, length 15cm gripping white during peel test) with Teflon sandwiched state (R) resin sheet (t = 0.2 mm), the superposition of unvulcanized rubber sheet.
[0281]
It said portion Teflon® resin sheet is sandwiched, an unvulcanized rubber sheet which is superimposed, with the EVA film is sandwiched between, at 180 ° C. with 100 ton press molding machine 10 minutes was pressed (the press), crosslinked rubber sheet (laminate) having a thickness of 2mm was prepared.
Crosslinked rubber sheet (laminate) removing Teflon resin sheet from were T-peel test for crosslinked rubber sheet (laminate).
[0282]
Example
1-2 instead of the EVA film except using the SMEVA film was performed in the same manner as in Example 1-1.
[0283]
[Comparative Example 1]
Except for not using EVA films was performed in the same manner as in Example 1-1.
[0284]
[Example
2-1] (Preparation of a composition comprising a VNB-EPT)
As a first step, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), 100 parts by weight of 30 seconds containing the ENB-EPT of kneaded, and then to this, FEF carbon 80 parts by weight (Asahi 60G: manufactured by Asahi carbon Co., Ltd.), magnesium oxide 5 parts by weight (Mag 150: manufactured by Kyowa chemical industry Co., Ltd.), 1 part by weight of stearic acid (beads stearic acid Tsubaki, manufactured by NOF Corp.), 50 parts by weight of process oil (Diana process PS430 manufactured by Idemitsu Kosan Co., Ltd.), and the mixture was kneaded for 2 minutes at 140 ° C.. Thereafter, performs cleaning to increase the ram, further, subjected to 1 minute kneading, discharged at about 0.99 ° C., to obtain a first phase of the formulation.
[0285]
Next, as a second step, the blend obtained in the first stage, 8 Inchiro - Le (Nippon Roll Co., Ltd., before the surface temperature 50 ° C. of the roll, the surface temperature of 50 ° C. of the rear roll, front roll wound rotational speed 16 rpm, the rotational speed 18 rpm) of the rear roll, this masterbatch (DCP-40c containing 40 wt% of dicumyl peroxide as the organic peroxide component of 10.2 parts by weight, Kayaku It was obtained Akzo Co., Ltd.) (organic peroxide converted at 4.1 parts by weight) were added and kneaded to uncrosslinked resin composition for 10 minutes (rubber compound) (composition containing ENB-EPT).
[0286]
(Preparation of a composition comprising a NBR, as well as the preparation of the laminate,
evaluation) preparing a composition comprising NBR, as well as the preparation of the laminate, for evaluation, ENB-EPT instead of a composition comprising a VNB-EPT except using a composition comprising, it was carried out in the same manner as in example 1-1.
[0287]
[Example
2-2] except using the SMEVA film instead of the EVA film was performed in the same manner as in Example 2-1.
[0288]
[Comparative Example 2]
Except for not using EVA films was performed in the same manner as in Example 2-1.
Evaluation results of Examples and Comparative Examples are shown in Table 3.
The scope of the claims
[Requested item 1]Olefin rubbers layer (A),
an ethylene-vinyl acetate copolymer, silane modified ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymers and ionomers, and ethylene-methacrylic acid copolymer and ionomer an adhesive resin layer containing one or more selected from the group consisting of (B),
a layer (C) comprising a rubber containing a group 15 element
laminate comprising a structure which is formed by laminating in this order.
[Requested item 2]
The adhesive resin layer (B) is laminated body according to claim 1 comprising at least one element selected from the group consisting of ethylene-vinyl acetate copolymer and silane-modified ethylene-vinyl acetate copolymer.
[Requested item 3]
It said layer (C) is laminated body according to claim 1 or 2 comprising a rubber containing a nitrogen atom.
[Requested item 4]
It said layer (C) is a nitrile rubber, laminate according to any one of claims 1 to 3 containing at least one element selected from the group consisting of hydrogenated nitrile rubber and urethane rubber.
[Requested item 5]
It said layer (C) is laminated body according to any one of claims 1 to 3 containing a nitrile rubber.
[Requested item 6]
The olefin-based rubber layer (A), the laminate according to any one of claims 1 to 5, containing an ethylene-alpha-olefin-non-conjugated polyene copolymer.
[Requested item 7]
The ethylene-alpha-olefin-non-conjugated polyene copolymer has a 5-vinyl-2-norbornene (VNB) derived constituent units of the laminate of claim 6.
[Requested item 8]
The laminate according to any one of claims 1 to 7, the hose having as at least a part.
[Requested item 9]
For the automotive, motorcycle, industrial machinery, used in any of the applications for construction equipment or agricultural machinery, hose according to claim 8.
[Requested item 10]
And said layer (A) and the layer (C), comprising the step of adhering the said layer (B), method for producing a laminate according to any one of claims 1 to 7.