JP2002038074A - Coating material for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an underbody coating material for a vehicle exhibiting excellent chipping resistance, vibration-damping properties, rustproof properties and weather resistance even when it is thin and cured at a low temperature for a short time. SOLUTION: The coating material for a vehicle comprises a silyl group- containing ethylene/α-olefin/non-conjugated polyene random copolymer rubber having a constituting unit derived from at least one terminal vinyl group- containing norbornene compound, a kind of non-conjugated polyene, and bearing a hydrolyzable silyl group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition containing an ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group, and its use. The present invention relates to a coating material for vehicles such as an underbody coating material for automobiles and a body sealer which is coated for the purpose of rust and vibration damping.

[0002]

2. Description of the Related Art Conventionally, an underbody coat material has been provided on the floor and sides of an automobile to prevent damage due to gravel or the like that jumps up during running, to prevent rust, and to reduce vibration and noise.
In addition, each seam of the inner and outer panels where it is difficult to perform rust-prevention treatment due to the body structure is coated with a body sealer for the purpose of preventing rusting due to intrusion of moisture or moisture from rainwater, etc. Vinyl chloride sol is used as a material suitable for use.

In recent years, there has been a demand for thinner and more excellent rust prevention and vibration damping properties in order to reduce the weight of automobiles. There is a strong demand. Vinyl chloride sol is inexpensive and has the minimum physical properties required for these applications. However, under low-temperature baking conditions, gelation progresses slowly and sufficient rust prevention and chipping resistance (damage prevention) are obtained. It has the disadvantage that it cannot be obtained. In addition, the damping performance is not so high basically, and tends to be further reduced in accordance with the demand for thinning.

JP-A-8-41349 proposes a coating material for vehicles using a saturated hydrocarbon polymer having a reactive silicon group as a crosslinking group. This product has improved low-temperature baking properties, rust prevention properties, chipping resistance, vibration damping properties, etc. as compared with vinyl chloride sol, but none of these properties are still satisfactory. Further improvement has been desired in terms of vibration properties, and further improvements have been desired with respect to properties such as curing speed and weather resistance of the resulting coating film.

[0005]

Therefore, according to the present invention, the curing speed is high even under low-temperature baking conditions, the curing is strong, and a uniform and stable coating film can be formed even with a thin film thickness. It is an object of the present invention to provide a curable composition capable of forming a coating film having excellent chipping resistance, vibration damping property and weather resistance, for example, a coating material for vehicles.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the problems in the prior art as described above. As a result, the following specific silyl group-containing ethylene / α-olefin / It has been found that a coating material having the above-mentioned desired properties can be obtained by using a non-conjugated polyene random copolymer rubber, and the present invention has been accomplished.

That is, the present invention has at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II], which is a non-conjugated polyene, and has the following structure in the molecule: General formula [III]
Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by

[0008]

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Wherein n is an integer of 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms],

[0010]

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Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0012]

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[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] Which is a coating material for vehicles.

The present invention also has a structural unit derived from at least one norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], which is a non-conjugated polyene, and has the following structure in the molecule: General formula [II
A curable composition comprising a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the formula (I): , Transport aircraft, civil engineering and construction,
A curable composition characterized by use in medical or leisure applications is shown.

The present invention also provides a non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], and the following general formula in the molecule: A sealing material comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the formula [III]. .

Further, the present invention provides a non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], wherein A potting material comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the general formula [III]. is there.

The present invention further has a structural unit derived from at least one norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], which is a non-conjugated polyene, and has the following structure in the molecule: General formula [III]
A non-vehicle coating material comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the formula:

Further, the present invention provides a non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], wherein An adhesive characterized by comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the general formula [III]. is there.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. The vehicle coating material of the present invention is:
Specific silyl group-containing ethylene α as described in detail below
-It is characterized by containing an olefin / non-conjugated polyene random copolymer rubber as a main vehicle component.

[Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber] The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is as follows: A specific silicon compound containing a hydrolyzable silyl group represented by the general formula [III] and a specific silicon compound is subjected to a hydrosilylation reaction with a specific ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ). (Hydrosilylation reaction).

[0021]

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In the general formula [III], R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably a monovalent hydrocarbon group having no aliphatic unsaturated bond. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and a part or all of the hydrogen atoms bonded to these carbon atoms Examples thereof include a group substituted with a halogen atom such as a fluorine atom.

X represents a hydride group (-H), a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group (-CONH ₂ ), an acid amide group, an aminooxy group ( -O
NH ₂ ), a thioalkoxy group, or an amino group (—NH
₂ ). Specific examples of a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an acid amide group, and a thioalkoxy group include the same groups as those of X in the general formula [IV] described below.

A is an integer of 0, 1 or 2, and is preferably 0 or 1. Ethylene, α-olefin and non-conjugated polyene random
Polymer Rubber (A ₀ ) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) used in the present invention comprises ethylene and
It is a random copolymer of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
Examples thereof include 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among them, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

These α-olefins may be used alone or in combination of two or more. The non-conjugated polyene used in the present invention has the following general formula [I] or [I
I] is a norbornene compound having a vinyl group at the terminal.

[0027]

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In the general formula [I], n is 0 to 10
R ¹ is a hydrogen atom or a carbon atom having 1 to 1
0 alkyl group, and as the alkyl group having 1 to 10 carbon atoms for R ¹ , specifically, a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, Examples include an octyl group, a nonyl group, and a decyl group.

R ^{2 is a} hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include the alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ .

[0030]

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In the general formula [II], R ^{3 is a} hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group of R ³ include the same alkyl groups as the specific examples of the alkyl group of R ¹ . As the norbornene compound represented by the general formula [I] or [II], specifically, 5-methylene-2-norbornene,
5-vinyl-2-norbornene, 5- (2-propenyl) -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-
Hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-
Pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene , 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among them, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5-
(5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

The above norbornene compound such as 5-vinyl
In addition to 2-norbornene, the following non-conjugated polyenes can be used in combination as long as the physical properties aimed at by the present invention are not impaired. Specific examples of such a non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Linear non-conjugated dienes such as 4,5-dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene,
5-methylene-2-norbornene, 5-isopropylidene-2-
Cyclic non-conjugated dienes such as norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene- And trienes such as 3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Ethylene / α comprising the above-mentioned components
-The olefin / non-conjugated polyene random copolymer rubber (A ₀ ) has the following properties. (I) Molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) is (a) ethylene And (b) a unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as α-olefin) in a proportion of 40/60 to 95/5, preferably 50/50 to 9
0/10, more preferably 55/45 to 85/15,
Particularly preferably, they are contained at a molar ratio of [(a) / (b)] of 60/40 to 80/20.

When the molar ratio is within the above range, a rubber composition which is excellent in heat aging resistance, strength characteristics and rubber elasticity and can provide a crosslinked rubber molded article excellent in cold resistance and processability is obtained. (Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) is 0.5 to 50 (g / 100).
g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 (g / 100 g), particularly preferably 1.5 to 25 (g / 1 g).
00g).

When the iodine value is within the above range, the content of the hydrolyzable silyl group can be adjusted to the desired content, and the compression set is excellent and the environmental deterioration resistance (= heat aging resistance) is excellent. Thus, a rubber composition capable of providing a crosslinked rubber molded article can be obtained. If the iodine value exceeds 50, it is disadvantageous in terms of cost, which is not preferable. (Iii) Intrinsic Viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) measured in decalin at 135 ° C. is 0.001 to 2 dl / g, preferably 0. 01 to 2 dl / g, more preferably 0.05 to 1 d
1 / g, more preferably 0.05 to 0.7 dl / g,
Particularly preferably, it is preferably 0.1 to 0.5 dl / g.

When the intrinsic viscosity [η] is within the above range, a rubber composition having excellent fluidity and capable of providing a crosslinked rubber molded article having excellent strength properties and compression set resistance can be obtained. (Iv) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) measured by GPC is 3 to 100, preferably 3. 3-7
5, more preferably 3.5 to 50.

When the molecular weight distribution (Mw / Mn) is within the above range, a rubber composition which is excellent in processability and can provide a crosslinked rubber molded article having excellent strength properties is obtained.
The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) used in the present invention has a polymerization temperature of 30 to 30 in the presence of a catalyst containing the following compounds (H) and (I) as main components. 60 ° C., especially 30-59 ° C., polymerization pressure 4-12 kgf / cm ² , especially 5-8 kgf / cm
^2. Under the condition of the molar ratio of the non-conjugated polyene and ethylene supplied (non-conjugated polyene / ethylene) of 0.01 to 0.2,
Ethylene, an α-olefin having 3 to 20 carbon atoms,
It can be obtained by random copolymerization with a norbornene compound having a terminal vinyl group represented by the general formula [I] or [II]. The copolymerization is preferably carried out in a hydrocarbon medium. (H) a soluble vanadium compound represented by VO (OR) _n X _3-n (where R is a hydrocarbon group, X is a halogen atom, and n is an integer of 0 or 1 to 3), Or a vanadium compound represented by VX ₄ (X is a halogen atom).

The soluble vanadium compound (H) is a component that is soluble in a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) _{a Xb} or V (OR) _c X _d
(Where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦
3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c
+ D.ltoreq.4), or an electron donor adduct thereof.

More specifically, VOCl ₃ , VO (OC _{2
H 5) Cl 2, VO (} OC 2 H 5) 2 Cl, VO (O-iso-
_{C 3 H 7) Cl 2,} VO (O-n-C 4 H 9) Cl 2, VO (O
C ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOCl ₃ , VO (O
—N—C ₄ H ₉ ) ₃ and VCl ₃ .2OC ₆ H ₁₂ OH. (I) R ′ _m AlX ′ _3-m (R ′ is a hydrocarbon group, X ′ is a halogen atom, m is 1
~ 3) an organoaluminum compound represented by the formula:

Specific examples of the organoaluminum compound (I) include trialkylaluminums such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethoxide, alkyl sesquichloride alkoxides such as butyl sesquichloride butoxide; R ¹ _0.5 Al
(OR ¹ ) a partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; a dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride; Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride and the like Dialkyl aluminum hydride, ethyl aluminum dihydride, propyl alcohol Partially hydrogenated alkyl aluminum such as alkylaluminum dihydride such as ruminium dihydride; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide Can be mentioned.

In the present invention, a soluble vanadium compound represented by VOCl ₃ among the above compound (H) and Al (OC ₂ H ₅ ) ₂ Cl among the above compound (I)
When a blend of / Al ₂ (OC ₂ H ₅ ) ₃ Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) Is preferred because an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) having an insoluble content of 1% or less can be obtained.

As a catalyst used in the above copolymerization, a so-called metallocene catalyst such as disclosed in JP-A-9-405 is used.
No. 86, the metallocene catalyst may be used. Silicon Compound The silicon compound used in the present invention has the following general formula [IV]
Is represented by

[0043]

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In the general formula [IV], R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably a monovalent hydrocarbon group having no aliphatic unsaturated bond; For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and a part or all of the hydrogen atoms bonded to these carbon atoms are fluorine atoms And the like.

X represents a hydride group (—H), a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group (—CONH ₂ ), an acid amide group, an aminooxy group ( -O
NH ₂ ), a thioalkoxy group, or an amino group (—NH
₂ ). Examples of the halogen group include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, a propoxybutoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a phenoxy group. And the like. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

Examples of the ketoxime group include an acetoxymate group, a dimethyl ketoxime group, a diethyl ketoxime, a cyclohexyl ketoxmate group and the like. Examples of the amide group include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, and a diphenylamide group.

Examples of the acid amide group include a carboxylic acid amide group, a maleic acid amide group, an acrylic acid amide group,
And itaconic acid amide groups. Examples of the thioalkoxy group include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thioisopropoxy group, a sec-thiobutoxy group, a tert-thiobutoxy group, a thiopentyloxy group, a thiohexyloxy group, and a thiophenoxy group. .

Examples of the amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group and a diphenylamino group. Among these, alkoxyl groups, especially those having 1 to 4 carbon atoms.
Are preferred. A in the general formula [IV] is an integer of 0, 1 or 2, and is preferably 0 or 1.

Specific examples of the silicon compound represented by the general formula [IV] include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, diethylchlorosilane, phenyldichlorosilane, and diphenylchlorosilane. Kind;
Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butyldiethoxysilane, phenyldimethoxysilane; triacetoxysilane, methyldimethoxysilane Acyloxysilanes such as acetoxysilane and phenyldiacetoxysilane; ketoxies such as tris (acetoxymate) silane, bis (dimethylketoxime) methylsilane, bis (methylethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane Mate silanes; aminoxy silane,
Examples include aminooxysilanes such as triaminoxysilane; aminosilanes such as methyldiaminosilane and triaminosilane. Of these, alkoxysilanes are particularly desirable.

The silicon compound represented by the general formula [IV] is used in an amount of 0.01 to 5 mol per mol of the double bond in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ). , Preferably 0.05 to 3 mol. The hydrosilylation reaction is
The reaction is performed using a catalyst of a transition metal complex. As such a catalyst, for example, a Group VIII transition metal complex compound selected from platinum, rhodium, cobalt, palladium and nickel is effectively used. Of these, platinum-based catalysts such as chloroplatinic acid and platinum-olefin complexes are particularly preferred. In this case, the amount of the catalyst used is a catalytic amount, but is preferably 0.1 to 10,000 ppm as a metal unit with respect to the reactant (ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ), Preferably 1 to 100
0 ppm, particularly preferably 20 to 200 ppm.
The preferred temperature for this hydrosilation reaction is between 30 and
The temperature is 180 ° C, preferably 60 to 150 ° C. In addition, this hydrosilylation reaction can be performed under pressure, if necessary. The reaction time is about 10 seconds to 10 hours.

In this reaction, a solvent may or may not be used, but when used, an inert solvent such as ethers and hydrocarbons is preferable. In the present invention,
By the hydrosilylation reaction, ethylene α
-Containing a hydrolyzable silyl group as described below, wherein a SiH group of a silicon compound represented by the above general formula [IV] is added to a double bond in an olefin / non-conjugated polyene random copolymer rubber (A ₀ ). The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is obtained.

[0053]

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[0054]

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A hydrogen-modified siloxane represented by the following formula is added together with the hydrolyzable silyl group-containing compound represented by the above general formula [IV] to give a weather resistance, a slip property and a gas characteristic of siloxane. It is also possible to impart transparency.

[0056]

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(Wherein R ¹ is the same as R ¹ in the general formula [IV])
Similarly to the above, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably an alkyl group. Further, m is an integer of 5 to 200, particularly 10 to 1
An integer of 50 is preferred. [Other Compounds] The coating material for vehicles of the present invention may be used by further adding a curing catalyst, a plasticizer, a filler, other additives, and the like, if necessary. Specific examples of the curing catalyst are not particularly limited, and a commonly used silanol condensation catalyst is used.

Specific examples of such a curing catalyst include, for example, an organic tin compound, an organic titanate compound, an organic aluminum compound, an organic zirconium compound, an amine compound, an acid phosphate, a reaction product of an acid phosphate and an amine compound, Examples thereof include a saturated or unsaturated polycarboxylic acid or an acid anhydride thereof, a reaction product such as a salt of a carboxylic acid compound and an amine compound, and lead octylate.

Specific examples of the organotin compound include dibutyltin diacetate and dibutyltin dilaureate.
Dibutyltin maleate, dioctyltin maleate,
Tin carboxylate such as dibutyltin phthalate, tin octylate, tin naphthenate, dibutyltin diacetylacetonate
And a reaction product of dibutyltin methoxide, dibutyltin oxide and a phthalic acid ester.

Specific examples of the organic titanate compound include, for example, titanates such as tetrabutyl titanate, tetraisopropyl titanate, tetrapropyl titanate, and triethanolamine titanate; and chelate compounds such as titanium tetraacetylacetonate. . Specific examples of the organoaluminum compound include, for example, aluminum trisacetylacetona-
And organic aluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxy aluminum ethyl acetoacetate.

Specific examples of the organic zirconium compound include, for example, organic zirconium compounds such as zirconium tetraisopropoxide and zirconium tetrabutoxide, and chelate compounds such as zirconium tetraacetylacetonate. Specific examples of the amine compound include, for example, butylamine, monoethanolamine, triethylenetriamine, guanidine, 2-
Ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and the like.

The above-mentioned acidic phosphoric acid ester is a phosphoric acid ester containing -OP (= O) (OH)-, for example, (RO) _d -P (= O)-(OH _3-d (where d represents 1 or 2, and R represents an organic residue), and an acidic phosphoric acid ester such as an organic acidic phosphoric acid ester represented by the formula:

As specific examples of the organic acid phosphate, for example, (CH ₃ O) ₂ P (＝ O) OH, (CH
_{3 O) P (= O)} (OH) 2, (C 2 H 5 O) 2 P (=
_{O) OH, (C 2 H} 5 O) P (= O) (OH) 2,
[(CH ₃ ) ₂ CHO] ₂ P (＝ O) OH, (CH ₃ )
₂ CHOP (= O) (OH) ₂ , (C ₄ H ₉ O) ₂ P
(＝ O) OH, (C ₄ H ₉ O) P (＝ O) (OH) ₂ ,
(C ₈ H ₁₇ O) ₂ P (＝ O) OH, (C ₈ H ₁₇ O) P
_{(= O) (OH) 2} , (C 10 H 21 O) 2 P (= O) O
H, (C ₁₀ H ₂₁ O) P (＝ O) (OH) ₂ , (C ₁₃ H ₂₇
O) ₂ P (＝ O) OH, (C ₁₃ H ₂₇ O) P (＝ O) (O
H) ₂ , (HOC ₈ H ₁₆ O) ₂ P (＝ O) OH, (HO
C ₈ H ₁₆ O) P (＝ O) (OH) ₂ , (HOC ₆ H
₁₂ O) ₂ P (＝ O) OH, (HOC ₆ H ₁₂ O) P (=
O) (OH) ₂ , [(CH ₂ OH) (CHOH) O] ₂
P (= O) OH, [ (CH 2 OH) (CHOH) O] -
P (= O) - (OH ) 2, [(CH 2 OH) (CHO
_{H) C 2 H 4 O]} 2 P (= O) OH, [(CH 2 OH)
_{(CHOH) C 2 H 4 O} ] P (= O) (OH) 2 and the like.

These curing catalysts are used in an amount of 0 to 20 parts by weight based on 100 parts by weight of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
Use about parts by weight. The plasticizer is not particularly limited, and any commonly used plasticizer can be used. However, a plasticizer having good compatibility with various components blended in the coating material of the present invention is preferable. Specific examples of such a plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate; dioctyl adipate, dioctyl sebacate, and the like. Non-aromatic dibasic acid esters of
Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphoric esters such as tricrenylene phosphate and tributyl phosphate; paraffin chlorides; alkyl diphenyl, polybutene, hydrogenated polybutene, ethylene-α-olefin oligomer , Α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, hydrocarbon oil such as partially hydrogenated terphenyl And the like, and these can be used alone or in combination of two or more. These plasticizers can also be blended during the production of the polymer.

Among these, hydrocarbon compounds having no unsaturated group (specifically, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, etc.) are the compounds of the present invention. It is preferable because it has good compatibility with various components blended into the composition, has little effect on the curing speed of the composition, and has good weather resistance and is inexpensive.

These plasticizers may be used in place of the solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, etc. when introducing the reactive silicon group into the saturated hydrocarbon polymer.
The amount of the plasticizer used is 1 to 100 parts by weight of the component (A).
When used in the range of not more than 00 parts by weight, preferable results can be obtained. Specific examples of the filler include, for example, calcium carbonate, talc, diatomaceous earth, mica, kaolin, magnesium carbonate, vermiculite, titanium oxide, graphite, alumina, silica, glass balloon, shirasu balloon, silica balloon, calcium oxide, calcium oxide, Inorganic fillers such as magnesium oxide and silicon oxide; and organic fillers such as powdered rubber, recycled rubber, fine powder of thermosetting or thermoplastic resin, and hollow bodies such as polyethylene. These fillers are used in an amount of about 3 to 300 parts by weight based on 100 parts by weight of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).

Examples of the antioxidant include commonly used known antioxidants, for example, sulfur-based antioxidants, radical inhibitors, ultraviolet absorbers and the like. Examples of the sulfur-based antioxidants include mercaptans, salts of mercaptans, sulfides including sulfide carboxylate esters and hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like. Specific examples of such a sulfur-based antioxidant include 2-mercaptobenzothiazole, which is a mercaptan, and 2-mercaptan, which is a salt of mercaptan.
Zinc salts of mercaptobenzothiazole, sulfides such as 4,4'-thio-bis (3-methyl-6-t-butylphenol) and 4,4'-thio-bis (2-methyl-6
t-butylphenol), 2,2'-thio-bis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi (2,6- Dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2,2'-thio-bis (4-octylphenol)
Nickel, dilaurylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, ditridecylthiodipropionate, distearyl β, β′-thiodibutyrate, lauryl-stearylthiodipropionate, 2 2,2-thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenol) propionate], a polysulfide 2
-Benzothiazole disulfide, tinc dibutyl dithiocarbamate which is a dithiocarboxylate, tinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, tincdi-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, tincethyl-phenyl-dithiocarbamate, tincdimethyldithio Carbamates and thioureas 1
-Butyl-3-oxy-diethylene-2-thiourea,
Examples thereof include di-o-tolyl-thiourea, ethylene thiourea, and trilauryl trithiophosphate, which is a thiophosphite. When such a sulfur-based antioxidant is used in the composition of the present invention as compared with other antioxidants, it can significantly prevent degradation of the main chain due to heat, and can reduce surface tack (stickiness). Generation can be prevented.

Examples of the radical inhibitor include 2,2
-Methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] a phenolic radical inhibitor such as methane;
-Naphthylamine, α-naphthylamine, N, N'-sec-
Butyl-p-phenylenediamine, phenothiazine, N,
And amine radical inhibitors such as N'-diphenyl-p-phenylenediamine.

As the ultraviolet absorber, for example, 2- (2 ′)
-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4
-Piperidine) sebacate and the like. When the above antioxidant is compounded, the compounding amount is 0.1 parts by weight based on 100 parts by weight of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
About 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable.

Examples of the other additives include anti-sagging agents such as hydrogenated castor oil, organic bentonite and calcium stearate, coloring agents, anti-aging agents, adhesion-imparting agents,
Solvents and the like. The coating material of the present invention thus obtained is particularly useful as an underbody coat material or a body sealer for rust prevention and anti-vibration for vehicles, and conforms to recent demands of the automobile industry. .

[Curable Composition and Its Use] The composition containing the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber as the component (A) as described in detail above is as follows: Although it is particularly useful as a coating material for vehicles, it can be suitably used in other applications.

That is, the present invention has at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II], which is a non-conjugated polyene, and has the following structure in the molecule: General formula [III]
Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the formula (A)

[0073]

Embedded image

Wherein n is an integer of 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms],

[0075]

Embedded image

Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0077]

Embedded image

[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] Curable composition characterized by containing electric and electronic parts, transportation equipment, civil engineering and construction,
It is a curable composition suitably used for medical or leisure applications.

Examples of the application of electric / electronic parts include heavy electric parts, light electric parts, sealing materials, potting materials, coating materials or adhesive materials for circuits and boards of electric / electronic devices; repair materials for electric wire coatings. An insulating seal material for electric wire joint parts; a roll for OA equipment; a vibration absorber; or an encapsulating material for gel or a capacitor. The sealing material is, for example, a refrigerator, a freezer, a washing machine,
It is suitably used as a sealing material for gas meters, microwave ovens, steam irons, and earth leakage breakers.

The above potting material is suitable for potting, for example, a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistor, an electrical insulating component, a semiconductive component, a conductive component, a solar cell or a flyback transformer for a television. Used for The coating material is, for example, various circuit elements such as a high-voltage thick film resistor or a hybrid IC; HIC, an electrical insulating component; a semiconductive component;
Printed circuit; ceramic substrate; buffer material such as diode, transistor or bonding wire; semiconductive element; or optical fiber for optical communication.

The above-mentioned adhesive is suitably used, for example, for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. Examples of the use of the transport machine include a car, a ship, an aircraft, and a railway vehicle. Applications for automobiles include, for example, gaskets for automobile engines, sealing materials for electrical components or oil filters; bottling materials for igniter HICs or hybrid ICs for automobiles; coating materials for automobile bodies, automotive window glasses, engine control boards; Examples include a gasket such as a pan or timing belt cover, a molding, a headlamp lens, a sunroof seal, and an adhesive for a mirror.

Examples of the use of a ship include a wiring junction box, a sealing material for electric system parts or electric wires, and an adhesive for electric wires or glass. Examples of the use of the civil engineering construction include, for example, a joint joint of a glass screen method in a commercial building, a joint around a glass between a sash, an interior joint in a toilet, a washroom or a showcase, a joint around a bathtub, and a prefabricated house. Sealants for building materials used for expansion joints and sizing board joints; Sealants for double glazing; Sealants for civil engineering used to repair roads; Paints and adhesives for metals, glass, stone, slate, concrete or tile And an adhesive sheet, a waterproof sheet or a vibration-proof sheet.

The above medical uses include, for example, medical rubber stoppers, syringe gaskets, and rubber stoppers for reduced-pressure blood vessels. Examples of the leisure use include swimming members such as swimming caps, diving masks, and ear plugs; and gel buffer members such as sports shoes and baseball gloves.

Further, the composition according to the present invention can be used for electric / electronic parts, transportation equipment, civil engineering construction, leisure, etc.
It can be suitably used as a sealing material (sealing material), a potting material, a coating material, and an adhesive. That is, the present invention has a structural unit derived from at least one type of norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], which is a non-conjugated polyene, and has the following general formula [ III] silyl group-containing ethylene containing a hydrolyzable silyl group
A sealing material comprising a curable composition containing an α-olefin / non-conjugated polyene random copolymer rubber.

The present invention further provides a non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], and having the following structure in the molecule: A potting material comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the general formula [III]. is there.

The present invention further comprises a structural unit derived from at least one norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], which is a non-conjugated polyene, and General formula [III]
A coating material comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the formula (1). Other than).

The present invention further relates to a non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II], and having the following structure in the molecule: An adhesive characterized by comprising a curable composition containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the general formula [III]. is there.

[0088]

The coating material for a vehicle according to the present invention can meet the demands in the automobile industry associated with a low and short baking temperature corresponding to the weight reduction, resource saving and energy saving of an automobile. Even under the curing condition for a long time, it is possible to form a coating film which gives excellent rust-proofing property, vibration-proofing property and weather resistance.

[0089]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The composition of the copolymer rubber used in the examples and comparative examples,
Iodine value, intrinsic viscosity [η], molecular weight distribution (Mw / Mn)
Was measured or determined by the following method. (1) Composition of copolymer rubber The composition of the copolymer rubber was measured by ¹³ C-NMR method. (2) Iodine value of copolymer rubber The iodine value of the copolymer rubber was determined by a titration method. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber was measured in decalin at 135 ° C. (4) Molecular Weight Distribution (Mw / Mn) The molecular weight distribution of the copolymer rubber was determined by the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC.
w / Mn). For GPC, GMH-HT and GMH-HTL manufactured by Tosoh Corporation were used for the column, and orthodichlorobenzene was used for the solvent.

[0090]

[Production Example 1] [Silyl group-containing ethylene / propylene / 5-
Vinyl-2-norbornene random copolymer rubber (A-
Production of 1)] 100 liter of substantial internal volume equipped with stirring blades
Stainless steel polymerization vessel (stirring speed = 250 rpm)
Using ethylene, propylene and 5-vinyl-2
-Terpolymerization with norbornene was carried out. Polymerizer side
60 liters of hexane / hour and ethylene into the liquid phase
3.0 kg, 9.0 kg of propylene, 5-vinyl-2-no
Rubornene at a speed of 550 g and hydrogen at 70 litters.
Torr, VOCl as catalyst_Three95 mmol, Al (E
t)_TwoCl 443 mmol, Al (Et)_1.5Cl _1.5To
It was fed continuously at a rate of 127 mmol.

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) was obtained in a uniform solution state. Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping, followed by vacuum drying at 55 ° C. for 48 hours. Was performed.

The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) obtained as described above has a yield of 3.5 kg / hr and an ethylene content of 68 mol / h. %, The intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.2 dl / g, the iodine value (IV) was 15 (g / 100 g), and the Mw / Mn was 15.

To 100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) obtained as described above was added 0.3% by weight of a 2% toluene solution of chloroplatinic acid. Then, 1.5 parts by weight of methyldimethoxysilane was charged and reacted at 120 ° C. for 2 hours.
After the reaction, excess methyldimethoxysilane and the solvent (toluene) were distilled off, and a dimethoxysilyl group (-SiH
(OCH ₃ ) ₂ ) -containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1)
101 parts by weight were obtained.

[0094]

[Production Example 2] [Production of saturated hydrocarbon polymer (CA-1)] In a four-necked flask equipped with a stirrer and a nitrogen line, 560 ml of dried methylene chloride and n-hexane 11 were placed.
60 ml, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride were weighed to obtain a homogeneous mixed solution.
℃, isobutylene monomer 570ml under reduced pressure
Was charged through a Molecula sieves tube.

In the above reaction solution cooled to -70 ° C,
Under stirring, the polymerization catalyst solution (titanium tetrachloride 14
(ml / 80 ml of methylene chloride) was added all at once to initiate the polymerization. Once the temperature was raised to -54 ° C, the temperature was reduced to -7 in about 17 minutes.
The temperature was lowered to 0 ° C. About 20 minutes after the initiation of the polymerization, 132 g of 1,9-decadiene was added, and stirring was further continued at -70 ° C for 4 hours.

[0096] The yellowish reaction solution was added to 3 L of warm water (about 45 mL).
C) and stirred for about 2 hours, the organic layer was separated, and the washing with pure water was repeated three times. The colorless and transparent organic layer thus obtained was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having vinyl groups at both ends. Then, the vinyl group-containing isobutylene oligomer 400
g was dissolved in 200 ml of n-heptane, heated to about 70 ° C., and then methyldimethoxysilane 1.5 [eq / vinyl group], platinum (vinylsiloxane) complex 1 × 10 ⁻⁴ [eq /
And a hydrosilylation reaction was carried out. F
The reaction was traced by T-IR, and it was 1640 cm in about 4 hours.
The olefin absorption of ^-1 disappeared.

The reaction solution was concentrated under reduced pressure to obtain an isobutylene oligomer having a reactive silicon group at both terminals as shown below.

[0098]

Embedded image

[0099]

[Production Example 3] [Production of saturated hydrocarbon polymer (CA-2)] In the same manner as in Production Example 2, except that 24 g of allylmethylsilane was used instead of 1,9-decadiene. Thus, an isobutylene oligomer having a partially different structure of a production intermediate was obtained.

[0100]

Embedded image

[0101]

[Production Example 4] [Production of saturated hydrocarbon polymer (CA-3)] In a four-necked flask equipped with a stirrer and a nitrogen line, 560 ml of dried methylene chloride and n-hexane 11 were placed.
60 ml, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride were weighed to obtain a homogeneous mixed solution.
℃, isobutylene monomer 570ml under reduced pressure
Was charged through a Molecula sieves tube.

In the above reaction solution cooled to -70 ° C,
Under stirring, the polymerization catalyst solution (titanium tetrachloride 14
(ml / 80 ml of methylene chloride) was added all at once to initiate the polymerization. Once the temperature was raised to -54 ° C, the temperature was reduced to -7 in about 17 minutes.
The temperature was lowered to 0 ° C. After the start of the polymerization, stirring was continued for about 60 minutes. Transfer the yellow-colored reaction solution to 3 L of warm water (about 45 ° C).
The mixture was stirred for about 2 hours, the organic layer was separated, and washing with pure water was repeated three times. The thus obtained colorless and transparent organic layer was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having tertiary chloro groups at both ends.

Further, the isobutylene oligomer was heated at 170 ° C. under reduced pressure for 2 hours, whereby
A thermal dehydrochlorination reaction was performed to obtain an isobutylene oligomer having an isopropenyl group at both ends. Next, 400 g of the isobutylene-containing isobutylene oligomer thus obtained was dissolved in 200 ml of n-heptane, heated to about 100 ° C. in a pressure vessel, and then methyldichlorosilane 1.5 [eq / vinyl group] was added. Then, platinum (vinylsiloxane complex 1 × 10 ⁻⁴ [eq / vinyl group]) was added, and a hydrosilylation reaction was carried out.
At 0 hours, the olefin absorption at 1640 cm ^-1 disappeared. After cooling the reaction solution to 60 ° C., an excess amount of [/ methyldichlorosilane] methanol was added, and the mixture was stirred for about 4 hours to complete the methoxylation. The reaction solution was concentrated under reduced pressure to obtain an isobutylene oligomer having the following structure and having reactive silicon groups at both ends.

[0104]

Embedded image

[0105]

[Synthesis Example 1] [Synthesis of copolymer (B)] In 20 g of xylene heated to 110 ° C, 5.7 g of butyl acrylate, 65.1 g of methyl methacrylate, 13.3 g of stearyl methacrylate, γ-methacryloxypropyl 5.6 g of trimethoxysilane, 8.0 g of γ-mercaptopropyltrimethoxysilane, 5.0 g of azobisisobutyronitrile
And a solution of 22 g of xylene was added dropwise over a period of 6 hours, followed by a polymerization reaction for another 2 hours.
Thus, a copolymer (B) having a number average molecular weight (Mn) of 2,100 as determined by GPC (in terms of polystyrene) was obtained.

[0106]

Examples 1 to 5 The silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in Production Example 1 and the copolymer obtained in Synthesis Example 1 ( B) and a solid content ratio (weight ratio) of 60/40, and using an evaporator, perform devolatilization under reduced pressure and heating at 110 ° C. to obtain a transparent and viscous liquid having a solid content concentration of 99% or more. Obtained.

100 g of heavy calcium carbonate and 5 g of colloidal calcium carbonate were added to 100 g of the blend devolatilized polymer.
0 g, glass balloon (average particle size: 70 μm), 5 g, diisononyl phthalate, 100 g, anhydrous silica, 5 g, hindered phenol-based antioxidant, 2 g, calcium oxide: 10 g
g, 2 g of an aluminum chelate-based curing catalyst, 1 g of an aminosilane compound, and a silicone-based reactive diluent (Shin-Etsu Silicone Co., Ltd., AFP-1) are sufficiently kneaded with a planetary mixer, and the sample (A- 1) was obtained.

[0108]

Reference Examples 1 to 9 In place of the silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in Production Example 1, the rubber compositions were obtained in Production Examples 2 to 4. Saturated hydrocarbon polymers (CA-1) to (CA-3)
Except for the use of Examples 1 to 5, blended devolatilized polymers were prepared in the same manner as in Examples 1 to 5, and samples (CA-1) to (CA) used in Comparative Examples 1 to 9 in the same manner as in Examples 1 to 5. −
3) was obtained.

[0109]

Comparative Examples 1 to 3 100 g of heavy calcium carbonate and 50 g of colloidal calcium carbonate per 100 g of vinyl chloride resin
, 5 g of a glass balloon (average particle size 70 μm), 100 g of diisononyl phthalate, 3 g of a lead-based dehydrochlorination inhibitor, and 5 g of a urethane prepolymer were sufficiently kneaded with a planetary mixer, and used as a sample (CA-4) for Comparative Examples 1 to 3. I got

These samples were placed on a cationic electrodeposited steel sheet as shown in Table 1.
The composition was applied and cured by changing the film thickness and curing conditions as shown in Table 2 below, and chipping resistance, salt spray resistance, and vibration damping properties were examined by the following test methods. Further, the weather resistance and the curing speed of the coating film were evaluated as follows. The results are shown in Table 1 below. The test methods performed are as follows. (Chip resistance) Three kinds of nuts, M-4, were dropped on the coating film under the condition of a height of 2 m and a test piece angle of 45 °, and the weight of the nuts falling until the base material appeared below was indicated. (Salt spray resistance) A sample coated on a cationic electrodeposited steel plate at a predetermined film thickness is cross-cut until reaching the metal at the center of the sample, and is held in a salt spray test tank for 200 hours. The maximum peel width when peeled with cellophane tape was indicated. (Vibration resistance) JASO7006 Based on the vibration resistance test method for underbody coating materials for automobiles, measured temperature 25
From the resonance frequency (f ₀ ) of the secondary resonance point and the frequency (f ₂ , f ₁ ) of the 3 dB lowering part at ° C., the formula: d = (f ₂ −f ₁ )
The anti-vibration coefficient (d) was obtained based on / f ₀ and displayed. (Curing speed test) Tack-free time at medium temperature Apply the material to a thickness of 10 mm on a cationic electrodeposited steel sheet,
And the surface was touched with a finger at regular intervals to measure the tack free time. The tack free time is defined as the time when the material no longer transfers to the finger. (Weather resistance test) According to JIS B-7753, an accelerated weather resistance test was performed under the following conditions. Sunshine
Carbon arc weatherometer Irradiation / rain cycle 120 min irradiation / 18 min rain Black panel temperature 63 ° C ± 2 ° C, tank temperature: 40 ° C ± 2 ° C Irradiation time: 250 hours After this test, cracks or melting with the naked eye ◎: No cracks or dissolved portions were observed. ○: Cracks or dissolved portions were found to be significant. △: Cracks or dissolved portions were found to be very large. The evaluation of the weather resistance was expressed as x.

[0111]

[Table 1]

As can be seen from Table 1, the coating material for vehicles of the present invention has excellent chipping resistance, anti-vibration properties, and salt-water resistance even when the curing conditions are low and short-term, and the coating thickness is small. It had sprayability and weather resistance, and had a very fast curing speed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09D 183/04 4J100 C09J 123/26 C09J 123/26 183/04 183/04 C09K 3/00 C09K 3/00 P 3/10 3/10 ZG F16J 15/10 F16J 15/10 YX (72) Inventor Yoshiharu Kikuchi 3 Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Invention Person: Yasushi Arino Big 3 Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Mitsuko Nagai 3rd Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Hirohide Sakaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture, Mitsui Chemicals Co., Ltd. (72) Inventor Masaki Sugawara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd. (72) Kishi, Inventor Husband 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. (72) Kaoru Ueno 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture 1190 Kasama-cho, Mitsui Chemical Co., Ltd. (72) Michio Sekine Inventor 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture AD03 AD05 AD06 AE03 AE04 AE05 4J002 BB201 FD020 FD050 FD070 FD140 FD200 GH01 GH02 GJ01 GL00 GN00 GQ00 4J038 CB101 CB111 CB141 CM021 GA01 GA02 GA06 GA09 GA12 GA13 GA15 NA03 PB07 GA04 GA04 GA31 JB09 LA05 LA07 MA02 MA04 MA05 MA06 NA19 NA20 4J100 AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q AR25R AU21R BA71H BA77H CA05 CA31 HB38 HC79 JA01 JA03 JA51 JA67

Claims (17)

[Claims] An unconjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II],
And a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula [III] in the molecule: Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Embedded image Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] The coating material for vehicles characterized by containing. 2. A non-conjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II],
And a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula [III] in the molecule: Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] The curable composition characterized by being used for electric / electronic parts, transportation equipment, civil engineering / architecture, medical treatment or recreational use. 3. The electric / electronic part is used for heavy electric parts,
Light electrical parts, sealing materials, potting materials, coating materials or adhesives for circuits and substrates of electric and electronic equipment;
3. A material for repairing an electric wire coating; an insulating sealing material for electric wire joint parts; a roll for OA equipment; a vibration absorber; or an encapsulating material for gel or a capacitor.
3. The curable composition according to item 1. 4. The curable composition according to claim 3, wherein said sealing material is used as a sealing material for refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, or earth leakage breakers. 5. The high-voltage transformer with a variable resistor section, wherein the potting material is a transformer high voltage circuit, a printed circuit board,
The curable composition according to claim 3, which is used for potting an electrical insulating component, a semiconductive component, a conductive component, a solar cell, or a flyback transformer for a television. 6. The coating material is a high-voltage thick film resistor or a circuit element of a hybrid IC; a HIC; an electrically insulating part; a semiconductive part; a conductive part; The curable composition according to claim 3, which is used for coating a buffer material of a wire; a semiconductive element; or an optical fiber for optical communication. 7. The curable composition according to claim 3, wherein the adhesive is used for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. 8. The curable composition according to claim 2, wherein the use of the transport machine is a use of an automobile, a ship, an aircraft or a railway vehicle. 9. The use of the automobile is as follows: a sealing material for a gasket, an electric component or an oil filter of an automobile engine; a botting material for an igniter HIC or a hybrid IC for an automobile; an automobile body, a window glass for an automobile, or an engine control board. The curable composition according to claim 8, wherein the curable composition is an adhesive for a gasket for an oil pan, a gasket for a timing belt cover, a molding, a headlamp lens, a sunroof seal or a mirror. 10. The curable composition according to claim 8, wherein the use of the ship is a wiring junction box, a sealing material for electric system parts or electric wires; or an adhesive for electric wires or glass. object. 11. The civil and architectural uses include a joint joint of a glass screen method in a commercial building, a joint around a glass between a sash, an interior joint in a toilet, a washroom or a showcase, a joint around a bathtub, a prefabricated joint. Sealants for building materials used for expansion joints for exterior walls for houses and joints for sizing boards; sealing materials for double-glazed glass; sealants for civil engineering used for road repair; metals, glass,
The curable composition according to claim 2, wherein the curable composition is used for a paint / adhesive for stone, slate, concrete or tile; or an adhesive sheet, a waterproof sheet, or a vibration-proof sheet. 12. The curable composition according to claim 2, wherein the medical use is a sealing material for a medical rubber stopper, a syringe gasket, or a rubber stopper for a reduced-pressure blood vessel. 13. The curable composition according to claim 2, wherein the leisure use is a swimming member for a swimming cap, diving mask or earplugs; or a gel cushioning member for sports shoes or baseball gloves. Composition. 14. A non-conjugated polyene represented by the following general formula [I]:
Or silyl group-containing ethylene having at least one type of norbornene compound having a terminal vinyl group represented by [II] and having a hydrolyzable silyl group represented by the following general formula [III] in the molecule:・ Α-
Olefin / non-conjugated polyene random copolymer rubber Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] The sealing material characterized by comprising the curable composition containing these. 15. A non-conjugated polyene represented by the following general formula [I]:
Or silyl group-containing ethylene having at least one type of norbornene compound having a terminal vinyl group represented by [II] and having a hydrolyzable silyl group represented by the following general formula [III] in the molecule:・ Α-
Olefin / non-conjugated polyene random copolymer rubber Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ], Comprising a curable composition comprising: 16. A non-conjugated polyene represented by the following general formula [I]:
Or silyl group-containing ethylene having at least one type of norbornene compound having a terminal vinyl group represented by [II] and having a hydrolyzable silyl group represented by the following general formula [III] in the molecule:・ Α-
Olefin / non-conjugated polyene random copolymer rubber Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] The coating material for non-vehicles characterized by comprising the curable composition containing this. 17. A non-conjugated polyene represented by the following general formula [I]:
Or silyl group-containing ethylene having at least one type of norbornene compound having a terminal vinyl group represented by [II] and having a hydrolyzable silyl group represented by the following general formula [III] in the molecule:・ Α-
Olefin / non-conjugated polyene random copolymer rubber Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. An adhesive comprising a curable composition comprising: