JP2003292697A - Rubber composition for building material gasket - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition capable of rapidly molding not only a water hose for a car excellent in low temperature flexibility and more reduced in high temperature compression permanent strain without damaging the original excellent thermal aging resistance, wheatherability or the like of EPDM but also a gasket for a building material excellent in silicone sealant antistaining properties, blooming resistance and low temperature flexibility and more reduced in high temperature compression permanent strain. <P>SOLUTION: This rubber composition for automotive hoses and building material gaskets comprises (A) an ethylene-propylene-7-methyl-1,6-octadiene random copolymer rubber produced by using a specific group-IVB transition metal catalyst, (B) a vulcanizing agent, and (C) a filler. The random copolymer rubber has a molar ratio of ethylene to propylene, an iodine value, an intrinsic viscosity, a strength ratio D, a B value, and a glass transition point, each in a specified range. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber composition for an automobile water hose and a building material gasket, and more specifically, it is capable of high-speed molding of an automobile water hose excellent in low-temperature flexibility and small in high-temperature compression set. Fast rubber composition for automobile water hoses, and silicone sealant stain resistance, blooming resistance,
TECHNICAL FIELD The present invention relates to a rubber composition for a building material gasket having a high vulcanization rate, which is capable of molding a building material gasket having excellent low-temperature flexibility and small high-temperature compression set at high speed.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene / propylene / non-conjugated diene copolymer rubber (hereinafter sometimes referred to as EPDM) has excellent weather resistance, ozone resistance and heat aging resistance, so that it can be used in automobile radiators. It is often used for water hoses such as tar hoses and heat hoses. However, since EPDM has a slow vulcanization rate, a vulcanization accelerator and a vulcanization aid are added to a rubber composition used for an automobile water hose in order to increase the vulcanization rate. Two or more vulcanization accelerators and vulcanization aids are used in combination. As described above, the conventional vulcanization process of the rubber composition for automobile water hoses is complicated because various vulcanization accelerators are used. Even if such a complicated vulcanization process is adopted, there is a limit in increasing the vulcanization speed, and the productivity of automobile water hoses has not been sufficiently improved. Further, the conventional rubber composition for automobile water hoses has a problem that it is necessary to use various kinds of vulcanization accelerators together, which hinders rationalization of the measuring process and the like.

[0003] In addition, since an automobile water hose is exposed to cold and high temperatures and subjected to a load, it is required to have excellent low temperature flexibility and small high temperature compression set. However, although the conventional EPDM composition has good low temperature flexibility, it is still insufficient and there is room for improvement. Further, the conventional EPDM composition has a small high temperature compression set, but there is room for improvement because there is a demand from the automobile industry to further reduce the high temperature compression set.

By the way, since EPDM is excellent in weather resistance, ozone resistance and heat aging resistance, it is often used in building material gaskets.

However, the building material gasket is often used by being combined with a silicone sealant,
Contamination to silicone sealants can be problematic. This silicone sealant contamination is affected by the types of vulcanization accelerator and process oil blended in the EPDM composition.

According to a test with a silicone rubber maker, MBTS (dibenzotidyl disulphide) is a vulcanization accelerator which does not stain the silicone sealant.
ZnBDC (Zinc dibutyldithiocarbamate), Zn
EDC (Zinc diethyldithiocarbamate), ZnEP
DC, CBS (N-cyclohexyl-2-benzothiazolyl sulfenamide), CMBT can be mentioned, and if a small amount is added, MBT, EU (2-mercaptoimidazoline)
It is said that it can be used.

However, these vulcanization accelerators have a problem that the vulcanization rate is slow or they are easily bloomed. Therefore, the conventional rubber composition for a building material gasket containing EPDM as a main component has a problem that the vulcanization rate is slow because the above-mentioned vulcanization accelerator is used and the productivity of the building material gasket is poor. Further, the EPDM composition having a high vulcanization rate and good productivity has a problem of silicone sealant contamination.

As the process oil, a medium-high viscosity paraffinic process oil is said to be good against silicone sealant contamination.

Further, since the gasket for building materials is exposed to cold and high temperatures and subjected to a load, it is required to have excellent low temperature flexibility and small high temperature compression set. However, although the conventional EPDM composition has good low temperature flexibility, it is still insufficient and there is room for improvement. Further, the conventional EPDM composition has a small high temperature compression set, but there is room for improvement to further reduce the high temperature compression set.

Therefore, it has been desired to develop a rubber composition for automobile water hoses, which is excellent in low-temperature flexibility and can be used for high-speed molding of automobile water hoses having high-temperature compression set and high vulcanization rate. Further, it is desired to develop a rubber composition for a building material gasket having a fast vulcanization rate, which has excellent silicone sealant stain resistance, blooming resistance, low-temperature flexibility, and enables high-speed molding of a building material gasket having a small high-temperature compression set. It is rare.

[0011]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and it does not impair the excellent heat aging resistance, weather resistance and the like which EPDM originally has, and the low temperature. It is excellent in flexibility and can be used for high-speed molding of automobile water hoses with lower high temperature compression set.
An object of the present invention is to provide a rubber composition for automobile water hoses having a high vulcanization rate.

Further, the present invention is a rubber for a building material gasket having a fast vulcanization rate, which is excellent in silicone sealant stain resistance, blooming resistance, low temperature flexibility, and can form a building material gasket having a small high temperature compression set at a high speed. The purpose is to provide a composition.

[0013]

SUMMARY OF THE INVENTION A first rubber composition for automobile water hoses according to the present invention comprises ethylene, propylene and 7-
A rubber composition comprising a random copolymer rubber (A) containing methyl-1,6-octadiene, a vulcanizing agent (B) and a filler (C), wherein the random copolymer (A ), (I) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 55/45 to 80/20, (ii) the iodine value is in the range of 7 to 30, and (ii)
i) The intrinsic viscosity [η] measured in decalin at 135 ° C is 2
dl / g <[η] <6 dl / g, and (iv) Tαβ T in ¹³ C-NMR spectrum.
The intensity ratio D to αα (= Tαβ / Tαα) is 0.5 or less, and the (B) ¹³ C-NMR spectrum and the B value calculated from the following formula are 1.00 to 1.50, (Vi) The glass transition temperature Tg determined by DSC is -53.
It is characterized by being below ℃.

B = P _OE / (2P _E · P _O ) In the above formula, P _E is ethylene excluding the ethylene unit derived from the 7-methyl-1,6-octadiene component in the random copolymer rubber. Is the mole fraction of the component, P
_O is the mole fraction of the propylene component contained in the random copolymer rubber, and P _OE is the propylene / total number of dyad chains in the random copolymer rubber.
It is the ratio of the number of ethylene chains.

A second rubber composition for automobile water hoses according to the present invention comprises ethylene, propylene, and
A rubber composition comprising a random copolymer rubber (A) containing 7-methyl-1,6-octadiene, a vulcanizing agent (B) and a filler (C), the random copolymer In the presence of a Group IVB transition metal catalyst-based catalyst in which the rubber (A) is composed of a Group IVB transition metal compound (a) containing a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound (b), Ethylene, propylene, 7
-Copolymerized with -methyl-1,6-octadiene,
And (i) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 55/45 to 80/20, (ii) the iodine value is in the range of 7 to 30, and (iii)
Intrinsic viscosity [η] measured in decalin at 135 ° C is 2dl
/ G <[η] <6 dl / g
(Iv) Tαα of Tαβ in ¹³ C-NMR spectrum
The intensity ratio D (= Tαβ / Tαα) is 0.5 or less, and the B value calculated from the (v) ¹³ C-NMR spectrum and the above formula is 1.00 to 1.50,
(Vi) The glass transition temperature Tg determined by DSC is −53 ° C. or less.

The first rubber composition for a building material gasket according to the present invention comprises ethylene, propylene and 7-methyl-.
A rubber composition comprising a random copolymer rubber (A) composed of 1,6-octadiene, a vulcanizing agent (B) and a filler (C), wherein the random copolymer (A) is ,
(I) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 60/40 to 75/25,
(Ii) the iodine value is in the range of 7 to 30, and (iii) 13
Intrinsic viscosity [η] measured in 5 ° C decalin is 2 dl / g
<[Η] <6 dl / g in the range represented by (iv)
^The intensity ratio D (= Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum is 0.5 or less,
(V) The B value calculated from the ¹³ C-NMR spectrum and the above formula is 1.00 to 1.50, and (vi) D
The glass transition temperature Tg determined by SC is −53 ° C. or less.

The second rubber composition for building material gasket according to the present invention is a random copolymer rubber (A) comprising ethylene, propylene and 7-methyl-1,6-octadiene, and a vulcanizing agent. A rubber composition comprising (B) and a filler (C), wherein the random copolymer rubber (A) contains a group IVB transition metal compound containing a ligand having a cyclopentadienyl skeleton. A copolymer of ethylene, propylene and 7-methyl-1,6-octadiene in the presence of a Group IVB transition metal catalyst system catalyst comprising (a) and an organoaluminum oxy compound (b), and , (I) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 60/40 to 75/25, (ii) the iodine value is in the range of 7 to 30, and (iii)
Intrinsic viscosity [η] measured in decalin at 135 ° C is 2dl
/ G <[η] <6 dl / g
(Iv) Tαα of Tαβ in ¹³ C-NMR spectrum
The intensity ratio D (= Tαβ / Tαα) is 0.5 or less, and the B value calculated from the (v) ¹³ C-NMR spectrum and the above formula is 1.00 to 1.50,
(Vi) The glass transition temperature Tg determined by DSC is −53 ° C. or less.

The IVB used in the production of the random copolymer (A) constituting the rubber composition for automobile water hoses and the rubber composition for building gaskets.
The group transition metal compound (a) is preferably a zirconium compound containing a ligand having a cyclopentadienyl skeleton.

The random copolymer rubber (A) comprises a zirconium compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound (b) and an organoaluminum compound (c).
Ethylene obtained using Group IVB transition metal catalyst
Propylene-7-methyl-1,6-octadiene copolymer rubber is particularly preferred.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The rubber composition for an automobile water hose and the rubber composition for a building material gasket according to the present invention will be specifically described below.

The rubber composition for automobile water hoses and the rubber composition for gaskets for building materials according to the present invention contain a specific random copolymer rubber (A), a vulcanizing agent (B) and a filler (C). I will do it.

Random Copolymer Rubber (A) The random copolymer rubber (A) used in the present invention may be ethylene, propylene and 7-methyl-1,6-octadiene (hereinafter sometimes referred to as MOD). ) And.

The random copolymer rubber (A) is obtained by copolymerizing ethylene, propylene and MOD in the presence of a specific Group IVB transition metal catalyst system catalyst, and has a specific composition and characteristics. Have. In particular, a random copolymer rubber (A) obtained by copolymerizing ethylene, propylene and MOD in the presence of a Group IVB transition metal catalyst-based catalyst containing a specific zirconium catalyst component is preferable. Details of the method for producing the random copolymer rubber (A) will be described later.

The random copolymer rubber (A) used in the present invention has the following composition and properties.

(I) The random copolymer rubber (A) used in the rubber composition for automobile water hoses has a molar ratio of ethylene and propylene (ethylene / propylene) in the range of 55/45 to 80/20. . When a random copolymer rubber (A) having a molar ratio of ethylene and propylene (ethylene / propylene) in the above range is used, a rubber composition capable of providing an automobile water hose excellent in low-temperature flexibility. Is obtained.

The random copolymer rubber (A) used in the rubber composition for building gaskets has a molar ratio of ethylene and propylene (ethylene / propylene) of 60/4.
It is in the range of 0 to 75/25. When the random copolymer rubber (A) having a molar ratio of ethylene and propylene (ethylene / propylene) in the above range is used, a rubber composition capable of providing a building material gasket excellent in low-temperature flexibility is obtained. can get.

(Ii) The random copolymer rubber (A) used in the rubber composition for automobile water hoses and the rubber composition for building material gaskets has an iodine value in the range of 7 to 30. When the random copolymer rubber (A) having an iodine value in the above range is used, a rubber composition having a high vulcanization rate, which can provide an automobile water hose and a building material gasket having a small high-temperature compression set, can be provided. can get.

EPDM in which the diene component is MOD (hereinafter sometimes abbreviated as MOD-EPDM) and diene component in 5-ethylidene-2-norbornene (hereinafter referred to as ENB
EPDM (hereinafter, ENB-)
(Sometimes abbreviated as EPDM) with the same iodine value, the vulcanization rate of MOD-EPDM is more than twice as fast.

The V-th component containing the vanadium catalyst component
ENB-E produced using a Group B transition metal catalyst-based catalyst
Even if PDM has a high diene content, if the diene content exceeds 4 mol%, the effect of improving the vulcanization rate is lost.
On the other hand, MOD-EPD produced using a Group IVB transition metal catalyst-based catalyst containing a specific zirconium catalyst component
M can accelerate the vulcanization rate in proportion to the diene content until the diene content becomes 7 mol%.

The V-th component containing a vanadium catalyst component
ENB-E produced using a Group B transition metal catalyst-based catalyst
When the iodine value of PDM is increased in order to accelerate the vulcanization rate, the low temperature flexibility is proportionally deteriorated. On the other hand, MOD-EPDM produced by using a Group IVB transition metal catalyst-based catalyst containing a specific zirconium catalyst component
Has excellent low temperature flexibility regardless of its iodine value.

(Iii) The random copolymer rubber (A) used in the rubber composition for automobile water hoses and the rubber composition for building material gaskets has an intrinsic viscosity [η] measured in 135 ° C. decalin of 2 dl / g <. [Η] <6 dl /
It is in the range represented by g. In these applications, the filler (C) content is often large, but when the random copolymer rubber (A) having an intrinsic viscosity [η] in the above range is used, the tensile strength is high. Moreover, a rubber composition capable of providing an automobile water hose and a building material gasket having a small high temperature compression set is obtained.

(Iv) The random copolymer rubber (A) used in the rubber composition for automobile water hoses and the rubber composition for building materials has a strength ratio D (= Tαβ / of Tαβ to Tαα in the ¹³ C-NMR spectrum. T
αα) is 0.5 or less, preferably 0.1 or less, more preferably 0.05 or less.

The strength ratio D of the random copolymer rubber (A) used in the present invention is ¹³ C according to the following method.
-Calculate based on the measurement result of the NMR spectrum.

That is, the above ¹³ C-NMR is a JEOL-GX270 NMR measuring apparatus manufactured by JEOL Ltd., and a mixed solution of hexachlorobutadiene / d ₆ -benzene = 2/1 volume ratio with a polymer concentration of 5% by weight is used. , 67.8MH
z ₆ at 25 ° C. based on d ₆ -benzene (128 ppm).

Analysis of the NMR spectrum is carried out by Lindemann
Dams Proposal (Analysis Chemistry 43, p1245 (197
1)), J.C.Randall (Review Macromolecular Chemistry
 Physics, C29, 201 (1989))
It was

Here, regarding the strength ratio D, ethylene
The propylene / 7-methyl-1,6-octadiene copolymer rubber will be described.

In this case, in the ¹³ C-NMR spectrum, the peak appearing at 45 to 46 ppm is assigned to Tαα, and the peak appearing at 32 to 33 ppm is assigned to Tαβ. The intensity ratio D is calculated.

The intensity ratio D thus obtained is generally the ratio of the 1,1 addition reaction of propylene followed by the 2,1 addition reaction, or the 1,2 addition reaction of propylene, followed by the 1,2 addition reaction. It is considered to be a measure of the rate at which an addition reaction occurs. Therefore, the larger the strength ratio D value, the more irregular the bonding direction of the monomer copolymerizable with ethylene. On the contrary, the smaller the D value is, the more regular the bonding direction is. The higher the regularity, the easier the molecular chains are to aggregate, and the better the physical properties such as strength may be. Therefore, in the present invention, the smaller the D value is, the more preferable.

Copolymerizing ethylene, propylene and 7-methyl-1,6-octadiene in the presence of a Group IVB transition metal catalyst system catalyst containing a specific Group IVB transition metal catalyst component such as zirconium. Therefore, ethylene / propylene / 7-methyl- whose strength ratio D is 0.5 or less
A 1,6-octadiene copolymer rubber can be obtained.

However, even when ethylene, propylene, and 7-methyl-1,6-octadiene are copolymerized in the presence of a Group VB transition metal catalyst-based catalyst containing a vanadium catalyst component, the strength ratio D is It is not possible to obtain an ethylene / propylene / 7-methyl-1,6-octadiene copolymer rubber having a ratio of 0.5 or less.

(V) The random copolymer rubber (A) used in the rubber composition for automobile water hoses and the rubber composition for building materials has a B value calculated by ¹³ C-NMR spectrum and the following formula. Is 1.00 to 1.
50, preferably 1.02 to 1.50, more preferably 1.02 to 1.45, particularly preferably 1.02 to 1.50.
40.

B = P _OE / (2P _E · P _O ) In the above formula, P _E is 7 in the random copolymer rubber.
Is the content mole fraction of the ethylene component excluding the ethylene unit derived from the -methyl-1,6-octadiene component, and P _O
Is the mole fraction of the propylene component contained in the random copolymer rubber, and P _OE is the ratio of the number of propylene / ethylene chains to the total number of dyad chains in the random copolymer rubber.

This B value is an index showing the distribution state of each monomer in the copolymer chain, and is JCRandall (Macro
molecules, 15, 353 (1982)), J. Ray (Macromolecules,
Based on the report of 10,773 (1977)), P _E , P _O, and P _OE defined as above are determined, and the B value is calculated from the above equation.

The larger the above B value, the shorter the blocky chain of ethylene or propylene, the more uniform the distribution of ethylene and propylene, and the narrower the compositional distribution of the copolymer. Also, the smaller the B value, the wider the composition distribution of the copolymer, and when such a copolymer is to be used after being vulcanized, it has a higher strength than a copolymer having a narrow composition distribution. It is not preferable because sufficient physical properties are not expressed.

By copolymerizing ethylene, propylene and 7-methyl-1,6-octadiene in the presence of a Group IVB transition metal catalyst system catalyst containing a specific Group IVB transition metal catalyst component. , The above B value is 1.00 to 1.
50 is ethylene propylene 7-methyl-1,6-
An octadiene copolymer rubber can be obtained.

However, even if ethylene, propylene and 7-methyl-1,6-octadiene are copolymerized in the presence of a Group IVB transition metal catalyst system catalyst containing a titanium catalyst component, the B value in the above range is It is not possible to obtain an ethylene / propylene / 7-methyl-1,6-octadiene copolymer rubber having However, this Group IVB transition metal catalyst-based catalyst does not include a Group IVB transition metal catalyst component containing a ligand having a cyclopentadienyl skeleton.

(Vi) The random copolymer rubber (A) used in the rubber composition for automobile water hoses and the rubber composition for building material gaskets is DSC (differential scanning calorimeter).
The glass transition temperature Tg determined in 1. is −53 ° C. or lower.

When the random copolymer rubber (A) having a glass transition temperature Tg of −53 ° C. or lower is used, a rubber composition capable of providing an automobile water hose and a building material gasket excellent in low temperature flexibility can be obtained. .

Random copolymer rubber (A) as described above
Is a particular zirconium, for example, as described above,
Group IVB containing a Group IVB transition metal catalyst component such as titanium
It is produced by copolymerizing ethylene, propylene, and MOD in the presence of a group-transition metal catalyst-based catalyst.

A preferred example of the Group IVB transition metal catalyst-based catalyst is a Group IVB transition metal catalyst-based catalyst comprising a zirconium compound containing a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound (b). And a zirconium compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound (b) and an organoaluminum compound (c).
Group IVB transition metal catalyst-based catalysts. In the present invention, the latter group IVB transition metal catalyst-based catalyst is particularly preferably used.

The Group IVB transition metal compound (a) containing a ligand having a cyclopentadienyl skeleton used in the present invention is a Group IV compound represented by the following general formula [I]:
Examples thereof include Group B transition metal compounds.

ML _X ... [I] In the above general formula [I], M is a Group IVB transition metal,
Zirconium is preferable, L is a ligand that coordinates with a Group IVB transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and a cyclopentadienyl skeleton is included. L other than the ligand having is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃
R (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom, and x is the valence of zirconium.

Specific examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and tetramethyl. Cyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group,
Alkyl-substituted cyclopentadienyl groups such as butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group; indenyl group;
4,5,6,7-tetrahydroindenyl group; fluorenyl group and the like.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Of these ligands that coordinate to zirconium, an alkyl-substituted cyclopentadienyl group is particularly preferable.

The zirconium compound represented by the above general formula [I] has a cyclopentadienyl skeleton-containing group 2
In the case of containing more than one, the group having two cyclopentadienyl skeletons is an alkylene group such as ethylene or propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group, or a dimethylsilylene group, a diphenylsilylene group, It may be bonded via a substituted silylene group such as a methylphenylsilylene group.

As the ligand other than the ligand having a cyclopentadienyl skeleton, as described above, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group. Group, SO ₃ R
(However, R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen.) Or a hydrogen atom, and specifically, the following groups or Atoms.

Examples of the above-mentioned hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Group;
Examples thereof include aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and neophyll group.

As the above alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group.

Examples of the aryloxy group include a phenoxy group.

Examples of the halogen atom include atoms such as fluorine, chlorine, bromine and iodine.

Examples of the ligand represented by SO ₃ R include p-toluenesulfonato group, methanesulfonato group and trifluoromethanesulfonato group.

The Group IVB transition metal compound represented by the above general formula [I] is more specifically represented by the following general formula [II] when the valence of zirconium is 4, for example, a zirconium compound.

R ¹ _a R ² _b R ³ _c R ⁴ _d M ··· [II] (In the formula [II], M is zirconium and R ¹ is a group having a cyclopentadienyl skeleton. R ² , R ³ and R ⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom,
a is an integer of 1 or more, and a + b + c + d = 4. In the present invention, in the above general formula [II], R ² , R ³
A zirconium compound in which one of R ⁴ and R ⁴ is a group having a cyclopentadienyl skeleton, for example, a zirconium compound in which R ¹ and R ² are groups having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as diphenylmethylene, alkylidene groups such as isopropylidene, silylene groups, or dimethylsilylene, diphenylsilylene, methylphenylsilylene, and the like. It may be bonded via a substituted silylene group or the like. Also, R ³ and R ⁴
Is a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom.

Specific examples of the zirconium compound represented by the above general formula [II] will be given below. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium Dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium Mubis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta) Dienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) dichloride Ruconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methyl Phenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds,
Tri-substitutions include 1,2,3- and 1,2,4-substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, te
Includes isomers such as rt-.

In the present invention, the above zirconium compounds can be used alone or in combination of two or more kinds. The organoaluminum oxy compound (b) used in the present invention may be a conventionally known aluminoxane, or is a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. May be.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec. -Butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum and other trialkyl aluminums; tricyclohexyl aluminum, tricyclooctyl aluminum and other tricycloalkyl aluminums; dimethyl aluminum chloride, Diethyl aluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum aryloxy such as diethyl aluminum phenoxide Do and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.

Further, as an organoaluminum compound used in the production of aluminoxane, the following general formula [I
It is also possible to use isoprenylaluminum represented by II].

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [III] (where x, y, and z are positive numbers, and z ≧ 2x The above organoaluminum compounds are used alone or in combination.

As the solvent used in the production of the aluminoxane as described above, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane,
Hexane, heptane, octane, decane, dodecane, hexadecane, aliphatic hydrocarbons such as octadecane, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, Alternatively, the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides, among others,
Examples include hydrocarbon solvents such as chlorinated compounds and brominated compounds.

In addition, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons are particularly preferable. Examples of the organoaluminum compound (c) used in the present invention include the organoaluminum compound represented by the following general formula [IV].

R ⁵ _n AlX _3-n ... [IV] (In the formula, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is Is 1
It is 3. In the above formula [IV], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

The following compounds may be mentioned as specific examples of such an organoaluminum compound.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkylaluminums such as ethylhexylaluminum; Alkenylaluminums such as isoprenylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride. Alkyl aluminum sesquihalides such as chloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide Id diethyl aluminum hydride, alkyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (c), a compound represented by the following formula [V] can be used.

R ⁵ _n AlY _3-n ... [V] (In the formula, R ⁵ is the same as above, Y is a —OR ⁶ group,
OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group, -SiR
¹⁰ ₃ groups or —N (R ¹¹ ) AlR ¹² ₂ groups, and n is 1
Is 2, and R ⁶ , R ⁷ , R ⁸ and R ¹² are methyl groups,
An ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, R ⁹ is hydrogen, a methyl group,
It is an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. ) Specific examples of such an organoaluminum compound include the following compounds.

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

(Ii) A compound represented by R ⁵ _n Al (OSiR ⁷ ₃ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (CH 3) 3),
_{(Iso-C 4 H 9)} 2 Al (OSi (C 2 H 5) 3) and the like.

(Iii) A compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OAl
_{(C 2 H 5) 2)} , (iso-C 4 H 9) 2 Al (OAl (iso-C
₄ H ₉ ) ₂ ) etc.

(Iv) a compound represented by R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as (CH ₃ ) ₂ Al (N (C
_{2 H 5) 2), (} C 2 H 5) 2 Al (NH (CH 3)), (C
_{H 3) 2 Al (NH (} C 2 H 5)), (C 2 H 5) 2 Al [N
_{(Si (CH 3) 3)} 2], (iso-C 4 H 9) 2 Al [N (Si
(CH ₃ ) ₃ ) ₂ ] etc.

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (CH
₃ ) ₃ ) etc.

[0085]

[Chemical 1]

Among the organoaluminum compounds represented by the above general formulas [IV] and [V], R ⁵ ₃ Al and R ⁵ _n Al
A preferred example is an organoaluminum compound represented by (OR ⁶ ) _3-n , R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , wherein R ⁵ is an isoalkyl group and n = 2. Is particularly preferable. These organoaluminum compounds may be used alone or in combination of two or more.

The Group IVB transition metal catalyst-based catalyst containing the specific Group IVB transition metal catalyst component used in the present invention is
From a Group IVB transition metal compound (a) such as zirconium containing a ligand having a cyclopentadienyl skeleton as described above, an organoaluminum oxy compound (b), and optionally an organoaluminum compound (c) It is formed.

In the present invention, the zirconium compound as the Group IVB transition metal compound (a) is usually converted to about 0.
00005-0.1 mmol, preferably about 0.000
Used in an amount of 1-0.05 mmol.

In the organoaluminum oxy compound (b), the amount of aluminum atom in the organoaluminum oxy compound (b) is 1 mol based on 1 mol of the zirconium atom.
Usually about 1 to 10,000 moles, preferably 10 to 5,
It is used in an amount such that it is 000 mol.

Further, the organoaluminum compound (c)
Is usually used in an amount of about 0 to 200 mol, preferably about 0 to 100 mol, per 1 mol of aluminum atom in the organoaluminum oxy compound (b).

In the present invention, ethylene, propylene,
When copolymerizing with 7-methyl-1,6-octadiene, the above group IVB transition metal catalyst system catalyst
Group IVB transition metal compound (a), organoaluminum oxy compound (b), and further organoaluminum compound (c)
May be separately fed to the polymerization reactor, or before the copolymerization reaction, a Group IVB transition metal catalyst-based catalyst containing the Group IVB transition metal catalyst component is prepared in advance. Good.

FIG. 1 shows a process for preparing a Group IVB transition metal catalyst-based catalyst containing a zirconium catalyst component used in the production of the random copolymer rubber (A) used in the present invention.

Specific examples of the inert hydrocarbon medium used for preparing the Group IVB transition metal catalyst-based catalyst containing the Group IVB transition metal catalyst component such as zirconium are:
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. it can.

The mixing temperature at which the Group IVB transition metal compound (a), the organoaluminum oxy compound (b) and the organoaluminum compound (c) are mixed and contacted is usually -100 to 200 ° C, preferably -70. ~ 100 ° C
It is desirable that the range is.

The above copolymerization is usually carried out at a temperature of -20 to 200.
° C, preferably 0 to 150 ° C, particularly preferably 20 to 1
At 20 ° C., the pressure is usually atmospheric pressure to 100 kg / cm ² ,
Preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably carried out under conditions of atmospheric pressure 30 kg / cm ^2.

The molecular weight of the above random copolymer rubber can be adjusted by changing the polymerization conditions such as the polymerization temperature, and also by controlling the amount of hydrogen (molecular weight modifier) used. it can.

The polymerization can be carried out by any of batch method, semi-continuous method and continuous method, but continuous method is preferred. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The polymer immediately after the polymerization is recovered from the polymerization solution and dried by a conventionally known separation / recovery method to obtain a solid random copolymer rubber (A).

Vulcanizing Agent (B) Examples of the vulcanizing agent (B) used in the present invention include sulfur, sulfur compounds and organic peroxides.

Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and polymer polysulfide. Further, a sulfur compound which releases active sulfur at the vulcanization temperature and vulcanizes, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, etc. can also be used.

In the present invention, the sulfur or sulfur compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the random copolymer rubber (A). To be

When sulfur or a sulfur compound is used as the vulcanizing agent (B), it is preferable to use a vulcanization accelerator together. As the vulcanization accelerator, specifically, N-
Cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2-benzothiazolsulfenamide, 2-mercaptobenzothiazo-
2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide and other thiazole compounds; diphenyl Guanidine, triphenylguanidine, diorsonitrile guanidine,
Guanidine compounds such as orthonitrile biguanide and diphenylguanidine phthalate; acetaldehyde
-Aniline reactant, butyraldehyde-aniline condensate,
Aldehyde amines such as hexamethylene tetramine and acetaldehyde ammonia, or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, and diorthotolyl thiourea. Compounds: tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Thiuram-based compounds such as tetrabutylthiuram disulfide and pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyldithiocarbamate Examples thereof include dithioate compounds such as sodium, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; zanthate compounds such as zinc dibutylxanthate; compounds such as zinc white.

In the present invention, among the rubber compositions for building material gaskets, for glazing gaskets which are required to have resistance to silicone sealant contamination, a vulcanization accelerator with little silicone sealant contamination, such as MBTS or ZnBD.
C, ZnEDC, CBS and CMBT are preferable, and MBT and EU can be used in a small amount.

In the present invention, the vulcanization accelerator is 0.1 to 100 parts by weight of the random copolymer rubber (A).
It is used in a proportion of 20 parts by weight, preferably 0.2 to 10 parts by weight.

The organic peroxide may be any compound which is usually used for peroxide vulcanization of rubber. For example, dicumyl peroxide, di-t-butyl peroxide,
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide,
2,5-Dimethyl-2,5-di (t-butylperoxine)
Hexine-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy) -hexane, α, α'-bis ( t-butylperoxy-m-isopropyl) benzene and the like. Among them, dicumyl peroxide,
Di-t-butyl peroxide, di-t-butyl peroxy
-3,3,5-Trimethylcyclohexane is preferably used. These organic peroxides are used alone or in combination of two or more.

In the present invention, the organic peroxide is used in an amount of 0.1 parts by weight per 100 parts by weight of the random copolymer rubber (A).
It is used in a proportion of from 10 to 10 parts by weight, but it is desirable to appropriately determine the optimum amount according to the required physical property values.

When an organic peroxide is used as the vulcanizing agent (B), it is preferable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; diallyl phthalate and triallyl cyanurate. Examples thereof include allyl compounds such as G. and the like; other maleimide compounds; divinylbenzene and the like.

In the present invention, it is preferable to use sulfur or a sulfur compound as the vulcanizing agent (B), and it is desirable to use a vulcanization accelerator together.

Filler (C) The filler (C) used in the present invention includes a filler having a reinforcing property and a filler having no reinforcing property.

The reinforcing filler has an effect of enhancing mechanical properties such as tensile strength, tear strength and abrasion resistance of the vulcanized rubber. As such a filler, specifically,
Examples thereof include carbon black, which may be surface-treated with a silane coupling agent, silica, activated calcium carbonate, and fine talc powder. In the present invention, any carbon black that is usually used for rubber can be used regardless of its type.

A filler having no reinforcing property may increase the hardness of a rubber product without significantly affecting the physical properties,
Used to reduce costs. As such a filler, specifically, talc, clay,
Examples include calcium carbonate.

Of the rubber compositions for building material gaskets, fillers such as carbon black with little silicone sealant contamination are used for glazing gaskets which are required to have resistance to silicone sealant contamination.

In the present invention, the filler (C) is 20 to 20 parts by weight with respect to 100 parts by weight of the random copolymer rubber (A).
It is used in an amount of 200 parts by weight, preferably 50 to 150 parts by weight.

In the rubber composition for an automobile water hose according to the present invention, in addition to the above random copolymer rubber (A), vulcanizing agent (B) and filler (C), vulcanization is performed as described above. Accelerators and vulcanization aids can be blended, but in addition, softeners, processing aids, ethylene glycol activators, organic amine activators, heat anti-aging agents, UV absorbers and other rubber compounds The agent can be blended within a range that does not impair the object of the present invention.

In addition to the random copolymer rubber (A), the vulcanizing agent (B) and the filler (C), the rubber composition for a building material gasket according to the present invention is added as described above. Although a vulcanization accelerator and a vulcanization aid can be blended, in addition to them, a softening agent, a processing aid, a heat antiaging agent, an ultraviolet absorber, a tackifier and other rubber compounding agents can be used for the purpose of the present invention. Can be blended within a range that does not impair

Among the rubber compositions for building material gaskets, the use of glazing gaskets, which are required to have resistance to silicone sealant contamination, is similar to the case of the above-mentioned vulcanization accelerator and filler (C). A small amount of softening agent or the like is used.

The rubber composition for automobile water hoses and the rubber composition for building material gaskets according to the present invention can be prepared, for example, by the following method.

That is, the rubber composition for an automobile water hose and the rubber composition for a building material gasket according to the present invention are prepared by mixing a random copolymer rubber (A) and a filler (C) with a mixer such as a Banbury mixer. After kneading necessary additives such as a softening agent at a temperature of 80 to 170 ° C. for about 3 to 10 minutes, a vulcanizing agent (B) is used by using a roll such as an open roll. If necessary, a vulcanization accelerator or a vulcanization aid is additionally mixed, and the roll temperature is 40 to 80 ° C. and the mixture is 5 to 3
It can be prepared by kneading for 0 minutes and then dispensing. The rubber composition thus obtained is a ribbon-shaped or sheet-shaped rubber compound.

The rubber composition for automobile water hoses and the rubber composition for building gaskets according to the present invention are
The random copolymer rubber (A), the vulcanizing agent (B), the filler (C) and the above additives are directly supplied to an extruder heated to about 80 to 100 ° C., and a residence time is about 0.5. It is possible to granulate the mixture in about 5 minutes and prepare it in the form of pellets.

[0121]

The random copolymer rubber (A) composed of ethylene, propylene and 7-methyl-1,6-octadiene used in the present invention has a molar ratio of ethylene and propylene, an iodine value and an intrinsic viscosity [ [η], the strength ratio D and B value of Tαβ and Tαα in the ¹³ C-NMR spectrum, and the glass transition temperature Tg are in a specific range, so that a vulcanized rubber excellent in low-temperature flexibility can be provided, and , Vulcanization speed is fast.

Further, this random copolymer rubber (A)
Has excellent properties such as weather resistance, ozone resistance, and heat aging resistance.

The rubber composition for automobile water hoses according to the present invention comprises the above-mentioned random copolymer rubber (A), a vulcanizing agent (B), and a filler (C).
It is possible to perform high-speed molding of an automobile water hose having excellent low-temperature flexibility and small high-temperature compression set without deteriorating the excellent heat aging resistance, weather resistance and the like which DM originally has.

The rubber composition for a building material gasket according to the present invention contains the above random copolymer rubber (A), a vulcanizing agent (B), and a filler (C). A construction material gasket having excellent silicone sealant stain resistance, blooming resistance, low-temperature flexibility, and high-temperature compression set can be molded at high speed.

Since these rubber compositions have a high vulcanization rate and can complete vulcanization in a short time, the productivity of automobile water hoses and building material gaskets can be improved, and the vulcanization accelerator can be used. It is possible to reduce the production cost because the use amount of can be reduced.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

The evaluation test methods for the ethylene / propylene / diene copolymer rubber and the vulcanized rubber in Examples and Comparative Examples are as follows.

[1] Physical Property Test of Unvulcanized Rubber The physical property test of unvulcanized rubber was carried out in accordance with JIS K 6300. Mooney viscosity [ML _{1 + 4} (100 ° C.)], Mooney scorch time (t ₅ [min]) and tΔ ₃₀ [min] were determined. tΔ ₃₀ is said to represent the degree of vulcanization rate. In addition, the unvulcanized rubber was measured with a Monsanto oil tentering rheometer (ODR).
The torque change was measured at 50 ° C and 170 ° C, and t ₁₀ [min],
The t ₉₀ [min] was determined and used as the vulcanization rate. The shorter t ₉₀ is, the faster the vulcanization rate is.

[2] Tg Tg of ethylene / α-olefin / diene copolymer rubber
Was measured with a differential scanning calorimeter (DSC). This glass transition temperature is an index of the low temperature flexibility of the ethylene / α-olefin / diene copolymer rubber.

・ Temperature cycle in Tg measurement by DSC: 18 ° C. from room temperature (25 ° C.) to 20 ° C./min
After raising the temperature to 0 ° C. and maintaining it at 180 ° C. for 2 minutes, this sample was cooled to −80 ° C. at a rate of −20 ° C./min, and 2
Hold the sample at −80 ° C. for a minute, and then repeat this sample at 20 ° C. /
The temperature was raised at a rate of min to obtain the Tg of the sample.

[3] Tensile test A vulcanized rubber sheet is punched out and JIS K 6301 (198
3rd type dumbbell test piece described in 9 years)
Then, the test piece was used to comply with JIS K 6301 Clause 3
According to the specified method, the measurement temperature is 25 ° C., the pulling speed is 500.
Tensile test was performed under the condition of mm / min and 100% module
Russ (M₁₀₀ ), 300% modulus (M ₃₀₀ ), Tension
Stress at break T_B And tensile elongation at break E_B Was measured.

[4] Hardness test Hardness test is based on JIS K 6301 (1989)
And spring hardness H _S(JIS A hardness) is measured
It was

[5] Compression set test The compression set test was conducted according to JIS K 6301 (1989).
The high temperature compression set (CS) was determined in accordance with.

Trial of rubber composition for automobile water hose
Test conditions Heating temperature: 120 ° C, 135 ° C Time: 22 hours Load: 10.5 kg Testing conditions for rubber composition for building materials Heating temperature: 100 ° C Time: 22 hours Load: 10.5 kg [6] Aging test automobile water hose In the examples of the rubber compositions for use in the aging test, the aging test was performed by the air heating aging test at 100 ° C. and 135 ° C. for 70 hours, and the tensile strength (T _B ) change rate and the elongation (E
The rate of change of _B) and to determine the rate of change of the JIS A hardness (H _S).

In the examples of the rubber composition for building material gaskets, the aging test was carried out by performing an air heating aging test at 100 ° C. for 70 hours, and the retention ratio to the physical properties before aging, that is, the tensile strength retention ratio A _R (T _B ) And elongation retention A _R (E _B ) were determined. The rate of change was determined for JIS A hardness (H _S ).

[7] Antifreeze resistance test The antifreeze resistance test was carried out on a rubber composition for automobile water hoses. The antifreeze resistance test is JIS K 6
Performed according to 301, the rate of change of tensile strength (T _B), the rate of change of elongation (E _B), the change rate being determined and the volume expansion of the JIS A hardness (H _S).

[0137]

Reference Example 1 Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, ethylene, propylene and 7-methyl-1,6-octadiene were continuously copolymerized.

Specifically, first, dehydration-purified hexane, a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (concentration: 0.05 mmol / liter), and triisobutylaluminum were introduced into the polymerization vessel from the upper portion of the polymerization vessel. Hexane solution (concentration 17 mmol / l), hexane slurry solution of methylalumoxane (3 mg atom / aluminum atom /
Liter) and 7-methyl-1,6-octadiene in hexane (concentration: 0.25 liter / liter) were continuously supplied.

Further, ethylene and propylene were continuously fed into the polymerization vessel from the upper portion of the polymerization vessel. This copolymerization reaction was performed at 50 ° C.

Then, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
After the copolymer was separated from the solvent by steam stripping treatment, the temperature was reduced to 100 ° C and the pressure was reduced to 100 mmHg.
It was dried for 24 hours.

With the above operation, ethylene / propylene / 7
A methyl-1,6-octadiene copolymer was obtained.

The resulting copolymer [hereinafter referred to as MOD-EPD
M (1) may be referred to as a rubber, and is a rubber having a molar ratio of ethylene and propylene (ethylene / propylene).
Is 70/30, the iodine value is 20, and 135 ° C.
Intrinsic viscosity [η] measured in decalin is 2.4 dl / g
And the Mooney viscosity [ML _{1 + 4} (100 ° C)] is 70.
Met. In addition, Tα in ¹³ C-NMR spectrum
The intensity ratio D of β to Tαα is less than 0.01,
The B value was 1.12 and the glass transition temperature was -61 ° C.

The ethylene / propylene-5-ethylidene-2-norbornene copolymer rubber [E
The quality of NB-EPDM (1), (2)] is shown below.

ENB-EPDM (1) has a molar ratio of ethylene and propylene (ethylene / propylene) of 68 /.
32, the iodine value was 13, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.3 dl / g,
The Mooney viscosity [ML _{1 + 4} (100 ° C.)] was 68.

ENB-EPDM (2) has a molar ratio of ethylene and propylene (ethylene / propylene) of 68 /.
32, the iodine value was 22, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.3 dl / g,
The Mooney viscosity [ML _{1 + 4} (100 ° C.)] was 68. [Examples and Comparative Examples of Rubber Composition for Automotive Water Hose]

[0146]

Example 1 MOD-EPDM obtained in Reference Example 1
(1) 100 parts by weight and Zinc Hua No. 3 [Sakai Chemical Industry Co., Ltd.
5 parts by weight, 1 part by weight of stearic acid [manufactured by Kao Corporation], 135 parts by weight of FEF carbon black [filler, manufactured by Showa Cabot], and paraffin oil [PA-90 manufactured by Idemitsu Kosan Co., Ltd. ] 90 parts by weight and 1 part by weight of polyethylene glycol # 4000 [manufactured by Kao Corporation] were kneaded in a Banbury mixer having a capacity of 1.7 liters [manufactured by Kobe Steel, Ltd.] for 6 minutes to obtain 332 parts by weight of masterbatch. Got

Masterbatch 3 thus obtained
32 parts by weight, CBS (vulcanization accelerator, N-cyclohexyl-2-benzothiazolylsulhenamide) 0.5 parts by weight, ZnBDC (vulcanization accelerator, zinc dibutyldithiocarbamate) 1.5 parts by weight, TMTD (Vulcanization accelerator, tetramethyl thiuram disulfide) 0.5 part by weight, EU
(Vulcanization accelerator, 2-mercaptoimidazoline) 0.5 part by weight, morpholine disulfide (vulcanizing agent, 4,4'-dithiodimorpholine) 1.5 parts by weight and sulfur 0.4
After adding parts by weight and kneading with an 8-inch roll having a roll width of 20 inches (temperature of front roll and rear roll: 40 ° C.) for 15 minutes, the mixture is dispensed into a sheet shape, and at 150 ° C. for 15 minutes [for compression set measurement 20 minutes at 150 ℃, 15 for aging test
15 minutes at 0 ° C], 150 kg / cm ² press vulcanization,
A vulcanized sheet having a thickness of 2 mm was prepared.

The vulcanized sheet thus obtained was subjected to the above-mentioned physical property tests and the like according to the above-mentioned methods.

For the unvulcanized rubber composition before vulcanization, the Mooney viscosity [ML
_{1 + 4} (100 ° C)], t ₅ (121 ° C), tΔ ₃₀ (12
1 ° C.), t ₁₀ (150 ° C.) and t ₉₀ (150 ° C.) were determined.

The results are shown in Table 1.

[0151]

Comparative Examples 1 and 2 In Example 1, MOD-EPDM
Instead of (1), the above ENB-EPDM (1), ENB
The same procedure as in Example 1 was carried out except that EPDM (2) was used.

The results are shown in Table 1.

[0153]

[Table 1]

[0154]

Example 2 To 332 parts by weight of the masterbatch of Example 1, 0.5 parts by weight of CBS (vulcanization accelerator, N-cyclohexyl-2-benzothiazolylsulhenamide) and ZnBD were added.
C (vulcanization accelerator, zinc dibutyldithiocarbamate)
1.5 parts by weight, TMTD (vulcanization accelerator, tetramethylthiuram disulfide) 0.5 parts by weight, morpholine
Addition of 1.5 parts by weight of disulfide (vulcanizing agent, 4,4'-dithiodimorpholine) and 0.4 parts by weight of sulfur, and an 8-inch roll having a width of 20 inches (temperature of front roll and rear roll 40 ° C) ) For 15 minutes, then dispensed into a sheet form and kept at 150 ° C. for 20 minutes [1 for compression set measurement]
25 minutes at 50 ° C, 20 minutes at 170 ° C for aging test], 1
50 kg / cm ² press vulcanization was performed to prepare a vulcanized sheet having a thickness of 2 mm.

With respect to the obtained vulcanized sheet, the above-mentioned physical property tests and the like were conducted according to the above-mentioned methods.

For the unvulcanized rubber composition before vulcanization, the Mooney viscosity [ML
_{1 + 4} (100 ° C)], t ₅ (121 ° C), tΔ ₃₀ (12
1 ° C.), t ₁₀ (150 ° C.) and t ₉₀ (170 ° C.) were determined.

The results are shown in Table 2.

[0158]

Comparative Examples 3 and 4 In Example 2, MOD-EPDM
Instead of (1), the above ENB-EPDM (1), ENB
The same procedure as in Example 2 was carried out except that EPDM (2) was used.

The results are shown in Table 2.

[0160]

[Table 2]

[Examples and Comparative Examples of Rubber Composition for Building Material Gasket]

[0162]

Example 3 MOD-EPDM obtained in Reference Example 1
(1) 100 parts by weight and Zinc Hua No. 3 [Sakai Chemical Industry Co., Ltd.
5 parts by weight, 1 part by weight of stearic acid [manufactured by Kao Corporation], 110 parts by weight of FEF carbon black [filler, manufactured by Showa Cabot], and paraffin oil [PA-90 manufactured by Idemitsu Kosan Co., Ltd.] ] 75 parts by weight were kneaded for 6 minutes with a Banbury mixer [made by Kobe Steel, Ltd.] having a capacity of 1.7 liters to obtain 291 parts by weight of a masterbatch.

Masterbatch 2 thus obtained
To 91 parts by weight, 1.5 parts by weight of MBTS (vulcanization accelerator, dibenzotidyl disulfide), 2.5 parts by weight of ZnBDC (vulcanization accelerator, zinc dibutyldithiocarbamate),
0.5 parts by weight of TeEDC (vulcanization accelerator, tellurium diethyldithiocarbamate) and 0.7 parts by weight of sulfur were added, and the mixture was kneaded for 15 minutes with an 8-inch roll having a width of 20 inches (the temperature of the front roll and the rear roll was 40 ° C.). After that, it is dispensed into a sheet shape, and it is heated at 170 ° C for 15 minutes [for compression set measurement at 170 ° C for 25 minutes, and for aging test at 170 ° C for 15 minutes.
Min], 150 kg / cm ² press vulcanization, thickness 2 mm
A vulcanized sheet of was prepared.

With respect to the obtained vulcanized sheet, the above-mentioned physical property tests and the like were conducted according to the above-mentioned methods.

For the unvulcanized rubber composition before vulcanization, the Mooney viscosity [ML
_{1 + 4} (100 ° C)], t ₅ (121 ° C), tΔ ₃₀ (12
1 ° C.), t ₁₀ (170 ° C.) and t ₉₀ (170 ° C.) were determined.

The results are shown in Table 3.

[0167]

Comparative Examples 5 and 6 In Example 3, MOD-EPDM
Instead of (1), the above ENB-EPDM (1), ENB
The same procedure as in Example 3 was carried out except that EPDM (2) was used.

The results are shown in Table 3.

[0169]

[Table 3]

[0170]

Example 4 To 291 parts by weight of the masterbatch of Example 3, 1.5 parts by weight of MBTS (vulcanization accelerator, dibenzothidyl disulfide), ZnBDC (vulcanization accelerator, zinc dibutyldithiocarbamate) were added. 5 parts by weight and 0.7 parts by weight of sulfur were added, and the mixture was kneaded for 15 minutes with an 8-inch roll having a roll width of 20 inches (the temperature of the front roll and the rear roll was 40 ° C.), then the mixture was dispensed into a sheet form and heated at 170 ° C. Minutes [for compression set measurement at 170 ° C. for 25 minutes, for aging test at 170 ° C. for 15 minutes], 150 kg / cm ² press vulcanization to prepare a vulcanized sheet having a thickness of 2 mm.

The vulcanized sheet thus obtained was subjected to the above-mentioned physical property tests and the like according to the above-mentioned methods.

For the unvulcanized rubber composition before vulcanization, the Mooney viscosity [ML
_{1 + 4} (100 ° C)], t ₅ (121 ° C), tΔ ₃₀ (12
1 ° C.), t ₁₀ (170 ° C.) and t ₉₀ (170 ° C.) were determined.

The results are shown in Table 5.

[0174]

Comparative Examples 7 and 8 In Example 3, the MOD-EPDM
Instead of (1), the above ENB-EPDM (1), ENB
The same procedure as in Example 3 was carried out except that EPDM (2) was used.

The results are shown in Table 4.

[0176]

[Table 4]

[Brief description of drawings]

FIG. 1 is a catalyst for olefin polymerization used in producing a random copolymer rubber (A) composed of ethylene, propylene and 7-methyl-1,6-octadiene used in the present invention. It is explanatory drawing which shows an example of the preparation process of.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Honma Sei             3 Chikusaigan, Ichihara, Chiba Prefecture Mitsui Chemicals Stock Association             In-house F-term (reference) 4J002 BB151 DA037 DA046 DE237                       DG026 DJ017 DJ047 EK036                       EK046 EV046 EV166 FD017                       FD146 FD150 GL00 GL02                       GN00                 4J100 AA02P AA03Q AS11R CA05                       DA22 DA47 FA10 JA67

Claims (4)

[Claims] 1. Ethylene, propylene and 7-methyl-
A rubber composition comprising a random copolymer rubber (A) containing 1,6-octadiene, a vulcanizing agent (B) and a filler (C), wherein the random copolymer (A) is (I) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 60/40 to 75/25, (ii) the iodine value is in the range of 7 to 30, and (iii) in decalin at 135 ° C. Viscosity [η] measured by
Is in the range represented by 2dl / g <[η] <6dl / g, and (iv) Tαβ of Tαβ in the ¹³ C-NMR spectrum.
The intensity ratio D (= Tαβ / Tαα) is 0.5 or less, (v) the ¹³ C-NMR spectrum and the B value calculated from the following formula are 1.00 to 1.50, vi) A rubber composition for a building gasket, which has a glass transition temperature Tg determined by DSC of −53 ° C. or lower; B = P _OE / (2P _E · P _O ), where P _E is random. 7-methyl in copolymer rubber
Is the content mole fraction of the ethylene component excluding the ethylene unit derived from the -1,6-octadiene component, P _O is the content mole fraction of the propylene component in the random copolymer rubber, and P _OE is All dyads (d in random copolymer rubber
yad) The ratio of the number of propylene / ethylene chains to the number of chains]. 2. Ethylene, propylene and 7-methyl-
A rubber composition comprising a random copolymer rubber (A) comprising 1,6-octadiene, a vulcanizing agent (B) and a filler (C), wherein the random copolymer rubber (A) IVB containing a ligand having a cyclopentadienyl skeleton
Ethylene, propylene and 7-methyl-1,6 in the presence of a Group IVB transition metal catalyst-based catalyst comprising a Group transition metal compound (a) and an organoaluminum oxy compound (b)
-Octadiene is copolymerized, and (i) the molar ratio of ethylene and propylene (ethylene / propylene) is in the range of 60/40 to 75/25, and (ii) the iodine value is 7 to 30. In the range, (iii) intrinsic viscosity [η] measured in 135 ° C decalin
Is in the range represented by 2dl / g <[η] <6dl / g, and (iv) Tαβ of Tαβ in the ¹³ C-NMR spectrum.
The intensity ratio D (= Tαβ / Tαα) is 0.5 or less, (v) the ¹³ C-NMR spectrum and the B value calculated by the following formula are 1.00 to 1.50, and vi) A rubber composition for a building gasket, which has a glass transition temperature Tg determined by DSC of −53 ° C. or lower; B = P _OE / (2P _E · P _O ), where P _E is random. 7-methyl- in copolymer rubber
It is the content mole fraction of the ethylene component excluding the ethylene unit derived from the 1,6-octadiene component, P _O is the content mole fraction of the propylene component in the random copolymer rubber, and P _OE is the random All dyads in copolymer rubber (d
yad) The ratio of the number of propylene / ethylene chains to the number of chains]. 3. The rubber composition for a building gasket according to claim 2, wherein the Group IVB transition metal compound (a) is a zirconium compound containing a ligand having a cyclopetadienyl skeleton. . 4. The Group IVB transition metal catalyst-based catalyst comprises a zirconium compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound (b) and an organoaluminum compound (c). The rubber composition for a building material gasket according to claim 2.