JP2002097318A - Weather strip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a weather strip using an olefin-based polymer as a raw material, capable of forming on the surface a coating film of high adhesion using a water-based surface treatment agent. SOLUTION: This weather strip is obtained by curing an olefin-based copolymer-containing rubber composition comprising (A) an olefin-based copolymer with functional group composed of (a-1) an ethylene-derived structural unit, (a-2) a 3-10C α-olefin-derived structural unit, (a-3) a functional group- containing unsaturated compound-derived structural unit and, as necessary (a-4) a nonconjugated diene-based compound-derived structural unit and having an intrinsic viscosity [η] determined in 135 deg.C decalin of 0.1-10 dL/g and (B) a curing agent and/or crosslinking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weather strip, and more particularly to a weather strip, which can form a film having excellent adhesion on a surface even when an aqueous type treating agent is used, and has excellent mechanical properties. Regarding weather strip.

[0002]

2. Description of the Related Art Weather strips of automobiles are often coated with a solvent type urethane or silicone type surface treatment agent in glass run or the like so far, so that the required performance of slip and abrasion resistance is imparted. Have been. However, a solvent type urethane-based or silicone-based surface treatment agent is desired to switch to an aqueous type surface treatment agent from the viewpoints of environment, health and safety.

On the other hand, a weatherstrip is made of a non-polar thermoplastic elastomer or an ethylene / α-olefin-based copolymer as a raw material. In this case, since the polymer material is hydrophobic, a water-based surface is used. There are problems such as poor compatibility with the treatment agent and poor adhesion to the formed film.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a weatherstrip which can form a film having excellent adhesion even when an aqueous type surface treatment agent is used, using an olefin polymer as a material. Is to provide.

[0005]

According to the present invention, a weatherstrip having the following structure is provided to achieve the above object of the present invention. 1. (A) (a-1) a structural unit derived from ethylene,
(A-2) a structural unit derived from an α-olefin having 3 to 10 carbon atoms, (a-3) a structural unit derived from a functional group-containing unsaturated compound, and if necessary, (a-4) non-conjugated It has a structural unit derived from a diene compound and has an intrinsic viscosity [η] of 0.1 to 10 dl measured in decalin at 135 ° C.
A weatherstrip obtained by vulcanizing an olefin copolymer having a functional group of / g and a rubber composition containing an olefin copolymer containing a vulcanizing agent and / or a crosslinking agent (B). 2. Olefin copolymer having the above functional group (A)
Is 5 to 90 mol% of the structural unit (a-1), 5 to 50 mol% of the structural unit (a-2), 0.01 to 5 mol% of the structural unit (a-3), and a-4) is 0 to
2. The weatherstrip according to the above 1, which has 10 mol%. 3. The functional group-containing unsaturated compound derived from the structural unit (a-3) is represented by the following formula (1) and / or the following formula (2)
3. The weatherstrip according to the above 1 or 2, which is a compound represented by formula (1).

[0006]

CH ₂ = CR ^1- (CH ₂ ) _n -X Formula (1)

(In the formula (1), X represents —OR ¹ , —COO
H, —NHR ¹ , or —CONHR ^{1 represents} a functional group;
R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms;
６6. )

[0008]

Embedded image

(In the formula (2), R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y ¹ , Y ² and Y ³ represent
Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a functional group of -OR ¹ , -COOH, -NHR ¹ , or -CONHR ¹ , and among Y ¹ , Y ² , and Y ³ At least one is a functional group, and Y ¹ , Y ² , Y ³
When two or more are functional groups, they are connected to each other to form an acid anhydride (—O— (CO) —O—)
Alternatively, it may be an imide group (—CO—NH—CO—). R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, o is an integer of 0 to 2, and p is an integer of 0 to 5. ) 4. The functional group X in the above formula (1) or at least one of Y ¹ , Y ² and Y ^{3 in} the above formula (2)
4. The weatherstrip according to any one of the above 1 to 3, wherein the two functional groups are a -COOH group. 5. The functional group-containing unsaturated compound derived from the structural unit (a-3) is a compound represented by the formula (2).
4. The weatherstrip according to any one of 3. 6. (A) an olefin copolymer having a functional group according to any one of the above 1 to 5, (B) a vulcanizing agent and / or a crosslinking agent, and (C) ethylene / α- having no functional group.
A weather strip obtained from a rubber composition containing an olefin-based copolymer.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The weatherstrip of the present invention is:
(A) (a-1) a structural unit derived from ethylene (hereinafter, referred to as “
"Structural unit (a-1)"), (a-
2) a structural unit derived from an α-olefin having 3 to 10 carbon atoms (hereinafter sometimes referred to as “structural unit (a-2)”), and a structure derived from (a-3) a functional group-containing unsaturated compound. A unit (hereinafter sometimes referred to as “structural unit (a-3)”) and a structural unit derived from (a-4) a non-conjugated diene-based compound (hereinafter referred to as “structural unit (a-4)”). An olefin copolymer having a functional group having an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in decalin at 135 ° C., and (B) a vulcanizing agent and / or
Alternatively, it can be obtained by vulcanizing a rubber composition containing a crosslinking agent. Further, the rubber composition may contain (C) an ethylene / α-olefin-based copolymer having no functional group within a range not to impair the achievement of the object of the present invention.

In the olefin copolymer (A) having a functional group used in the present invention, the structural unit (a-1)
Is preferably contained in the range of 5 to 90 mol%, more preferably 10 to 85 mol%, particularly preferably 15 to 80 mol% in all the structural units. When the content ratio of the structural unit (a-1) is less than 5 mol%, it becomes difficult to copolymerize the functional group-containing cyclic olefin represented by the formula (2), and moreover, the mechanical properties of the obtained copolymer are reduced. Strength and abrasion resistance may decrease. On the other hand, when the proportion of the structural unit (a-1) exceeds 90 mol%, the obtained copolymer may not exhibit the behavior as an elastomer.

The structural unit (a-2) has 3 to 10 carbon atoms.
Are structural units derived from α-olefins. here,
Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-pentene-1, 1-hexene, 1-heptene, 1-octene,
-Decene, styrene, p-methylstyrene and the like. Among them, propylene, 1-butene, 1-hexene and 1-octene are preferably used, and propylene and 1-butene are most preferably used. These compounds can be used alone or in combination of two or more. When an α-olefin having 10 or less carbon atoms is used, the copolymerizability of the α-olefin with other monomers is improved.

The structural unit (a-2) is preferably contained in the range of 5 to 50 mol%, more preferably 10 to 45 mol%, and particularly preferably 15 to 40 mol% of all the structural units. Mol%. When the content ratio of the structural unit (a-2) is less than 5 mol%, the elasticity of the obtained copolymer may be insufficient. On the other hand, when the proportion of the structural unit (a-2) exceeds 50 mol%, the mechanical strength and abrasion resistance of the obtained copolymer may decrease.

The structural unit (a-3) is a structural unit derived from a functional group-containing unsaturated compound. Specifically, the structural unit represented by the formula (1) and / or the formula (2) Can be mentioned.

In the above formula (1), X represents —OR ¹ ,
-COOH, it represents a functional group of -NHR ¹ or -CONHR ^1, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms,, n represents an integer of 0 to 6.

Examples of the functional group-containing unsaturated compound represented by the formula (1) include vinyl methyl ether, ethyl vinyl ether, acrylic acid, acrylamide, N-methylacrylamide, N-ethylacrylamide, allyl alcohol, allyl methyl ether, Allyl ethyl ether, vinyl acetic acid, allylamine, N-methylallylamine, N-ethylallylamine, vinylacetamide, N
-Methylvinylacetic acid amide, N-ethylvinylacetic acid amide, methacrylic acid, methacrylamide and the like. Among them, acrylic acid, acrylamide, N-methylacrylamide, N-ethylacrylamide, allyl alcohol, vinyl acetic acid, allylamine, N-methylallylamine, N-ethylallylamine, vinylacetic acid amide, N-methylvinylacetic acid due to copolymerizability Amides and N-ethylvinylacetamide are preferred.

In the above formula (2), R^TwoIs the water
A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
Y¹, Y^Two, Y^ThreeAre each independently a hydrogen atom, carbon
A hydrocarbon group of the formulas 1 to 10, or -OR¹-COOH,
-NHR¹Or -CONHR ¹Y represents a functional group of
¹, Y^Two, Y^ThreeAt least one of which is a functional group;
Y¹, Y^Two, Y^ThreeWhen two or more are functional groups
Are the acid anhydrides formed by linking each other (-O
-(CO) -O-) or an imide group (-CO-NH-C
O-). R¹Is hydrogen or carbon number 1
A hydrocarbon group of 10 to 10, o is an integer of 0 to 2, p is 0 to 5
Indicates an integer.

Here, the hydrocarbon group having 1 to 10 carbon atoms in R ² includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, A decyl group can be mentioned. Further, as Y ¹ , Y ² and Y ³ , for example, hydrogen,
A hydrocarbon group having 1 to 10 carbon atoms, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group, an amino group, an N-methylamino group, an N-ethylamino group, an amide group, an N-methylamide group, and an N-ethylamide group. Can be mentioned.

The number of repetitions o is an integer of 0 to 2, and when o is 3 or more, it becomes difficult to copolymerize the unsaturated compound having a functional group with another monomer.

The functional group-containing unsaturated compound represented by the above formula (2)
Products include cyclopentadiene and unsaturated
Condensation with compound by Diels-Alder reaction
It can be manufactured by the following. Equation (2) shows
Specific examples of the functional group-containing unsaturated compound include 5,6-di
Methyl-5,6-dihydroxy-bicyclo [2.2.
1] -2-heptene, 5,6-dimethyl-5,6-dica
Ruboxy-bicyclo [2.2.1] -2-heptene,
5,6-diethyl-5,6-dicarboxy-bicyclo
[2.2.1] -2-heptene, 5,6-dimethyl-
5,6-bis (carboxymethyl) -bicyclo [2.
2.1] -2-Heptene, 5,6-diethyl-5,6-
Bis (carboxymethyl) -bicyclo [2.2.1]-
2-heptene, 5,6-dimethyl-5,6-bis (hydr
Roxymethyl) -bicyclo [2.2.1] -2-hepte
, 5,6-diethyl-5,6-bis (hydroxymethyl
Ru) -bicyclo [2.2.1] -2-heptene, 5,6
-Dimethyl-5,6-bis (aminomethyl) -bicyclo
[2.2.1] -2-heptene, 5,6-diethyl-
5,6-bis (aminomethyl) -bicyclo [2.2.
1] -2-heptene, 5,6-dimethyl-5,6-bis
(Aminopropyl) -bicyclo [2.2.1] -2-he
Putene, 5,6-dimethyl-5,6-bis (aminocal
Bonyl) -bicyclo [2.2.1] -2-heptene,
5,6-dimethyl-5,6-bis (N-methyl-amino
Carbonyl) -bicyclo [2.2.1] -2-hepte
, 5,6-dimethyl-5,6-bis (N-propyl-
Aminocarbonyl) -bicyclo [2.2.1] -2-he
Putene, 5,6-diethyl-5,6-bis (aminocar
Bonyl) -bicyclo [2.2.1] -2-heptene,
5,6-diethyl-5,6-bis (N-ethyl-amino
Carbonyl) -bicyclo [2.2.1] -2-hepte
5,6-dimethyl-bicyclo [2.2.1] -2-
Heptene-5,6-dicarboxylic imide, 5-methyl-
5-hydroxy-bicyclo [2.2.1] -2-hepte
, 5-methyl-5-carboxy-bicyclo [2.2.
1] -2-heptene, 5-ethyl-5-carboxy-bi
Cyclo [2.2.1] -2-heptene, 5-carboxy
-5-carboxymethyl-bicyclo [2.2.1] -2
-Heptene, 5-methyl-5-hydroxymethyl-bis
Black [2.2.1] -2-heptene, 5-ethyl-5-
Hydroxymethyl-bicyclo [2.2.1] -2-hep
Ten, 5-methyl-5-carboxymethyl-bicyclo
[2.2.1] -2-heptene, 5-ethyl-5-cal
Boxymethyl-bicyclo [2.2.1] -2-hepte
5-methyl-5-aminomethyl-bicyclo [2.
2.1] -2-Heptene, 5-ethyl-5-aminomethyl
Rubicyclo [2.2.1] -2-heptene, 5-methyl
Ru-5-aminopropyl-bicyclo [2.2.1] -2
-Heptene, 5-methyl-5-aminocarbonyl-bis
Black [2.2.1] -2-heptene, 5-methyl-5
N-methyl-aminocarbonyl-bicyclo [2.2.
1] -2-Heptene, 5-methyl-5-N-propyl-
Aminocarbonyl-bicyclo [2.2.1] -2-hep
Ten, 5-ethyl-5-aminocarbonyl-bicyclo
[2.2.1] -2-Heptene, 5-ethyl-5-N-
Ethyl-aminocarbonyl-bicyclo [2.2.1]-
2-heptene, 8,9-dimethyl-8,9-dicarboxy
Sil-tetracyclo [4.4.0.1 ^2,5. 1^7,10]-
3-dodecene, 8,9-diethyl-8,9-dicarboxy
Sil-tetracyclo [4.4.0.1 ^2,5. 1^7,10]-
3-dodecene, 8,9-dimethyl-8,9-bis (hydr
Roxylmethyl) -tetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,9-diethyl-
8,9-bis (hydroxylmethyl) -tetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-dimethyl-8,9-bis (aminomethyl) -tetra
Cyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
, 8,9-diethyl-8,9-bis (aminomethyl)
-Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8,9-dimethyl-8,9-bis (aminoca
Rubonyl) -tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,9-dimethyl-8,9-bi
(N-methyl-aminocarbonyl) -tetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-diethyl-8,9-bis (aminocarbonyl) -te
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-dode
Sen, 8,9-diethyl-8,9-bis (N-ethyl-
Aminocarbonyl) -tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-methyl-8-cal
Boxy-tetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-ethyl-8-carboxyl-tet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8-methyl-8-hydroxymethyl-tetracycline
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 8
-Ethyl-8-hydroxymethyl-tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-8-aminomethyl-tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-ethyl-8
-Aminomethyl-tetracyclo [4.4.0.1^2,5.
1^7,10] -3-Dodecene, 8-methyl-8-aminocar
Bonyl-tetracyclo [4.4.0.1^2,5. 1^{7 ,Ten}]
-3-dodecene, 8-methyl-8-N-methyl-amino
Carbonyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-ethyl-8-aminocarbo
Nyl-tetracyclo [4.4.0.1^2,5. 1^{7 ,Ten}]-
3-dodecene, 8-ethyl-8-N-ethyl-aminoca
Rubonyl-tetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene and the like.

The structural unit (a-3) has a content of 0.
It is preferably contained in the range of 01 to 5 mol%, more preferably 0.05 to 4 mol%, particularly preferably 0.1 to 3 mol%. If the content of the structural unit (a-3) is less than 0.01 mol%, the resulting copolymer will have reduced adhesion, compatibility, and coatability to metals, elastomers other than olefins, and resins. Sometimes. On the other hand, when the proportion of the structural unit (a-3) is more than 5 mol%, copolymerization with a monomer other than an olefin-based monomer may be difficult, and the obtained copolymer may have rubber elasticity as an elastomer. It is difficult to obtain, and as a result of using a large amount of the polymerization catalyst, it may be difficult to obtain a high molecular weight copolymer.

The structural unit (a-4) is a structural unit derived from a non-conjugated diene compound, and is contained in the copolymer as required. Specific examples of the non-conjugated diene-based compound from which the structural unit (a-4) is derived include 1,4
Linear non-cyclic dienes such as -hexadiene, 1,6-hexadiene and 1,5-hexadiene; 5-methyl-1,4
-Hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,
Branched acyclic diene such as 7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydromyrcene; tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo-
(2,2,1) -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5 And alicyclic dienes such as -cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene. These compounds can be used alone or in combination of two or more. Preferred examples of the non-conjugated diene include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.

The structural unit (a-4) is 0 to 0 in all the structural units.
It is preferably contained at a ratio of 10 mol%, more preferably 0 to 8 mol%, and particularly preferably 0 to 8 mol%.
~ 5 mol%. When the content ratio of the structural unit (a-4) is 1
If it exceeds 0 mol%, the catalytic activity is remarkably reduced, which is not preferable in terms of cost.

The olefin copolymer (A) having a functional group used in the present invention has an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in decalin at 135 ° C. And preferably 0.1 to 7 dl / g, more preferably 0.1 to 5 dl / g. When the intrinsic viscosity [η] is less than 0.1 dl / g, kneading when blending with another olefin copolymer rubber is difficult. On the other hand, when the intrinsic viscosity [η] exceeds 10 dl / g, the moldability of the copolymer decreases.

The olefin copolymer (A) having a functional group used in the present invention has a weight average molecular weight Mw in terms of polystyrene measured by a gel permeation chromatography method at 135 ° C. in an o-dichlorobenzene solvent. It is preferably from 1,000 to 3,000,000, more preferably from 3,000 to 1,000,000.
0, particularly preferably 5,000 to 700,000, and the number average molecular weight Mn in terms of polystyrene is 500 to 1,
00000, more preferably 1,000 to 500,000, particularly preferably 2,000.
00 to 300,000.

The glass transition temperature of the olefin copolymer (A) used in the present invention is preferably from -90 to
The temperature is 50C, more preferably -70 to 10C. Thereby, an elastomer having sufficient elasticity can be obtained. Here, the glass transition temperature of the olefin-based copolymer (A) can be measured by a scanning differential thermal analyzer (DSC).

The vulcanizing agent of the component (B) used in the present invention is not particularly limited. Examples thereof include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, and insoluble sulfur; sulfur chloride, selenium, tellurium, and the like. And inorganic sulfur vulcanizing agents such as morpholine disulfide, alkylphenol disulfides, thiuram disulfides, and dithiocarbamates. These vulcanizing agents can be used alone or in combination of two or more. The mixing ratio of the vulcanizing agent is usually 0.1 parts by weight with respect to 100 parts by weight of rubber.
10 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

A vulcanization accelerator can be used together with the vulcanizing agent. Such vulcanization accelerators include, for example, aldehyde ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine, di (o-tolyl) guanidine, o-tolylpiguanide; thiocarbanilide, di (o-tolyl) thiourea; N, N'-
Thioureas such as diethylthiourea, tetramethylthiourea, trimethylthiourea and dilaurylthiourea; mercaptobenzothiazole, dibenzothiazole disulfide, 2- (4-morpholinothio) benzothiazole, 2- (2,4-dinitrophenyl) Thiazoles such as) -mercaptobenzothiazole and (N, N'-diethylthiocarbamoylthio) benzothiazole;
-T-butyl-2-benzothiazylsulfenamide,
N, N'-dicyclohexyl-2-benzothiazylsulfenamide, N, N'-diisopropyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-
Sulfenamides such as benzothiazylsulfenamide; thiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra-n-butylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide; dimethylthiocarbamine Zinc acid, zinc diethylthiocarbamate, zinc di-n-butylthiocarbamate,
Carbamates such as zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium dimethylthiocarbamate and iron dimethylthiocarbamate; and xanthates such as zinc butylthioxanthate. These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is
Usually 0.1 to 20 parts by weight, based on 100 parts by weight of rubber,
Preferably it is 0.2 to 10 parts by weight.

[0029] In addition to the vulcanizing agent and the vulcanization accelerator, a vulcanization accelerating aid may be added as necessary. Examples of such vulcanization accelerating aids include metal oxides such as magnesium oxide, zinc white, litharge, rhododendron, and lead white; organic acids (salts) such as stearic acid, oleic acid, and zinc stearate; Of these, zinc white and stearic acid are particularly preferred. The vulcanization accelerating aid,
They can be used alone or in combination of two or more. The amount of the vulcanization accelerator is usually 0.5 to 20 parts by weight based on 100 parts by weight of the rubber.

Next, as the crosslinking agent in the component (B), for example, 1,1-di-tert-butylperoxy-3,
3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t Organic peroxides such as -butylperoxyisopropyl) benzene and the like. These crosslinking agents can be used alone or in combination of two or more. The compounding amount of the crosslinking agent is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the rubber.

A crosslinking aid can be used in combination with the crosslinking agent. As such a crosslinking aid, for example,
Sulfur or sulfur compounds such as sulfur and dipentamethylenethiuram tetrasulfide; ethylene di (meth) acrylate, polyethylene di (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, metaphenylene bismaleimide, toluylene bismaleimide, etc. Polyfunctional monomers; oxime compounds such as p-quinone oxime and p, p'-benzoylquinone oxime. These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is usually 0.5 parts by weight based on 100 parts by weight of rubber.
-20 parts by weight.

Further, a rubber composition for producing a weatherstrip may contain a reinforcing agent, a filler or a softening agent, which is a compounding chemical generally used for rubber. As the reinforcing agent, SRF, FEF, HA
Examples thereof include carbon black such as F, ISAF, SAF, FT, and MT, white carbon, and fine particle magnesium silicate. Examples of the filler include inorganic fillers such as calcium carbonate, magnesium carbonate, clay, and talc. These reinforcing agents and fillers can be used alone or in combination of two or more. The amount of filler
100 to 100 parts by weight of rubber, usually 10 to 200 parts by weight,
Preferably it is 10 to 100 parts by weight.

Examples of the softener include process oils such as aromatic oils, naphthenic oils and paraffin oils, vegetable oils such as coconut oil, and the like, which are commonly used for rubber.
Synthetic oils such as alkylbenzene oils and the like can be mentioned. Of these, process oils are preferable, and paraffin oil is particularly preferable. The above softeners can be used alone or in combination of two or more. The amount of the softener is usually 10 to 130 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the rubber.

Since the structural unit (a-3) of the olefin copolymer (A) having a functional group used in the present invention has a specific functional group, its vulcanized product is a polar elastomer or resin. Thus, a weatherstrip having excellent coatability can be obtained even when an aqueous urethane-based or silicone-based surface treatment agent is used.

The olefin-based copolymer (A) having a functional group is a copolymer (C) of a general ethylene-free copolymer having no functional group.
A rubber composition for producing a weatherstrip can be used in combination with an α-olefin-based copolymer. In this case, the weight ratio of the component (A) to the component (C) ((A) /
(C)) is usually 1/99 to 99/1, preferably 1/99 to 99/1.
99-50 / 50, more preferably 3 / 97-30 / 7
0.

The olefin copolymer (A) having a functional group may be a high molecular weight polymer or a liquid low molecular weight polymer.

Further, since it has high compatibility with non-olefin polymers, non-olefin elastomer materials such as nitrile rubber, chloroprene rubber, chlorinated polyethylene rubber, halogenated butyl rubber, acrylic rubber, ethylene-acryl copolymer It can also be suitably used by mixing with rubber, hydrogenated nitrile rubber, silicon rubber, fluorine rubber and the like.

The olefin-based copolymer (A) having the above functional groups can be produced as follows. When using a functional group-containing unsaturated compound, first,
Reacting an organometallic compound (hereinafter, referred to as a “specific organometallic compound”) with a metal selected from Group 2, 12, and 13 of the periodic table and a specific functional group-containing unsaturated compound; With this, the functional group of the specific functional group-containing unsaturated compound is masked.

Specific examples of the specific organometallic compound used in the masking treatment include diethyl zinc, dibutyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diisobutyl hydride and the like. Aluminum, diethylaluminum hydride, ethylaluminum dihydride, diethylaluminum ethoxide, ethylaluminum diethoxide, dibutylaluminum ethoxide, dibutylaluminum butoxide, diisobutylaluminum dibutoxide, diisobutylaluminum isopropoxide, diisobutylaluminum 2-ethylhexide, Isobutyl aluminum butoxide, isobutyl aluminum 2-ethylhexide, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquichloride, ethylaluminum dichloride, methylalumoxane, ethylalumoxane obtained by reaction of water or copper sulfate hydrate with trialkylaluminum And butylalumoxane. Of these, organoaluminum compounds are preferred, and particularly preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, ethylaluminum sesquichloride and the like.

The masking treatment, ie, the reaction between a specific functional group-containing unsaturated compound and a specific organometallic compound is carried out in the presence of an inert solvent or diluent and under an inert gas such as nitrogen gas, argon gas or helium gas. It is preferable to carry out in a gas atmosphere. Here, examples of the inert solvent or diluent include aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane; cyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, toluene and xylene. , Aromatic compounds such as chlorobenzene, dichloroethane and dichloromethane, and halogenated hydrocarbon compounds can be used.

The specific organometallic compound is used in an amount of 0.8 equivalent or more, preferably 0.9 to 1.5 equivalent, per equivalent of the functional group in the specific functional group-containing unsaturated compound. Is preferred. If this ratio is too small, a large amount of functional groups that are not masked remain, so that the catalytic activity may decrease in the polymerization treatment described below, and the polymerization reaction may not proceed sufficiently. The reaction conditions of a specific functional group-containing unsaturated compound and a specific organometallic compound are as follows:
Depending on the type of the specific organometallic compound and the specific functional group-containing unsaturated compound used, the reaction time is,
The reaction temperature is usually 2 minutes to 10 hours, preferably 10 minutes to 2 hours, and the reaction temperature is usually -10 to 60 ° C, preferably 1 to 10 hours.
0-40 ° C.

The specific functional group-containing unsaturated compound thus masked is preferably stored at a temperature of 30 ° C. or less until it is used before being subjected to the polymerization treatment. Reaction can be prevented from occurring. In addition, the specific functional group-containing unsaturated compound subjected to the masking treatment has a branched structure in order to increase the stability during storage when unreacted metal-carbon bonds are present in the masked compound. Isopropanol, se
Alcohols such as c-butanol, tert-butanol and 2-ethylhexanol, and 2,6-di-tert
Phenols such as -butylcresol, 2,6-di-tert-butylphenol, 2,6-dimethylcresol, and 2,6-dimethylphenol can also be added.

Then, the specific functional group-containing unsaturated compound subjected to the masking treatment, ethylene, a specific α-olefin, and a non-conjugated diene used as necessary are polymerized. In this polymerization, a catalyst comprising a transition metal compound, preferably a compound of a metal selected from Groups 4 and 5 of the periodic table, and an organoaluminum compound is used. As the catalyst, it is preferable to use a catalyst which gives a relatively random monomer arrangement in a copolymerization reaction of ethylene, α-olefin and non-conjugated diene.
Specific catalyst systems include the following.

(1) A catalyst system comprising a vanadium compound soluble in a hydrocarbon compound and an organoaluminum compound, wherein either the vanadium compound or the organoaluminum compound contains at least one chlorine atom. Also,
In this catalyst system, an oxygen-containing or nitrogen-containing electron donor such as an ester of an organic acid or an inorganic acid, an ether, an amine, a ketone, or an alkoxysilane can be further added to the vanadium compound and the organic aluminum compound.

(2) A catalyst system comprising a titanium or zirconium halide supported on silica or magnesium chloride and an organic aluminum. Here, as the titanium halide, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, or the like can be used. As the organic aluminum compound, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylalumoxane, or the like can be used. In this catalyst system, dioctyl phthalate, tetraalkoxysilane, diphenyldimethoxysilane, and the like can be further added to the above compound.

(3) The ligand is selected from titanium, zirconium, and halfnium having one or two cyclopentadienyl groups or indenyl groups having a substituent selected from hydrogen, an alkyl group, and an allyl group. A catalyst system comprising a transition metal compound of a selected metal and an organoaluminum compound containing at least 50 molar equivalents of methylalumoxane.

(4) A metallocene catalyst comprising bisalkyl-substituted or N-alkyl-substituted saltyl aldimine, titanium, zirconium or hafnium dichloride, and methylalumoxane (MAO).

The polymerization reaction is preferably carried out in the presence of a suitable solvent or diluent. As such a solvent or diluent, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof can be used. Specifically, butane, pentane, hexane, heptane, 2-butene, 2-methyl-
2-butene, cyclopentane, methylcyclopentane,
Cyclohexane, isooctane, benzene, toluene,
Xylene, chlorobenzene, dichloromethane, dichloroethane and the like can be mentioned. These solvents or diluents can remove 20p of water by distillation or adsorption.
pm or less.

The polymerization reaction is carried out at 0 to 150 ° C., particularly at 10 to 1
It is preferably carried out at a temperature of 00 ° C. In the polymerization reaction, a molecular weight regulator can be used as necessary, and specific examples thereof include hydrogen, diethylzinc, and diisobutylaluminum hydride. The reactor for performing the polymerization reaction may be any of a batch type and a continuous type. As the continuous reactor, a tube reactor, a tower reactor, a tank reactor, or the like can be used.

After the polymerization as described above, the resulting copolymer is subjected to a demasking treatment, whereby an olefin copolymer (A) having a functional group can be obtained. As a specific functional group-containing unsaturated compound,
When a specific functional group is a hydroxyl group or a carboxyl group, formic acid, oxalic acid, fumaric acid, lactic acid, dioctylmonophosphate, trifluoroacetic acid, dodecylbenzenesulfonic acid, nonylphenoxypolyethylene glycol monophosphate The demasking treatment can be performed using an acid having a relatively high acidity, such as an ester, a diphosphate of nonylphenoxypolyethylene glycol, a monophosphate of lauroxypolyethylene glycol, and a diphosphate of lauroxypolyethylene glycol.

On the other hand, when the specific functional group-containing unsaturated compound is a compound whose specific functional group is an amino group or an amide group, an alcoholate of t-butanol with lithium, sodium or potassium; amyl alcohol Alcoholates of octanoic acid with lithium, sodium or potassium; lithium or potassium salts of nonylphenol with strong basic alcoholates or alkali metal salts of phenol or organic carboxylic acids. Masking processing can be performed.

The copolymer solution containing the olefinic copolymer thus obtained is passed through an adsorption column filled with silica, alumina, diatomaceous earth, or the like, or added to the copolymer solution with water. It is preferable to remove the remaining demasking agent, polymerization catalyst and the like by adding a large amount of alcohol or the like and washing.

For the purpose of improving the stability of the olefin-based copolymer, a known phenol-based, phosphorus-based or sulfur-based antioxidant can be added to the copolymer solution.

After removing the solvent by blowing steam into the copolymer solution, solids are separated from the resulting slurry, and further separated using a screw-type squeezing machine, extruder, heating roll, or the like. By dehydration and drying, the olefin copolymer (A) having a solid functional group is obtained. Alternatively, the copolymer solution is concentrated by heating and then dried using a vented extruder to obtain an olefin-based copolymer (A) having a solid functional group.

According to the method described above, the functional group in the unsaturated compound having a specific functional group is masked with the specific organometallic compound, so that the functional group is reliably masked. Of the olefin-based copolymer (A) having a desired functional group can be surely produced.

The weather strip of the present invention is prepared by kneading the above-mentioned components using a conventionally known kneading machine, for example, an open roll mill, a Banbury mixer, a kneader, etc., to prepare an olefin rubber composition (compounded rubber). Then, the compounded rubber is formed into a desired shape by an extruder, and a high-frequency heating device, an air oven, a PC
The weather strip can be obtained by vulcanization using a heating device such as M or LCM. Further, a weather strip may be manufactured by a method of molding and vulcanizing in a mold using a vulcanizing apparatus known per se. Furthermore, a weatherstrip can be manufactured by molding and vulcanizing the compounded rubber using an injection molding apparatus.

When a film is formed on the surface of a weather strip using an aqueous type surface treating agent, an aqueous type surface treating agent is applied to the surface after molding the compounded rubber.
Thereafter, vulcanization and curing are performed. In this case, a vulcanization method using a high-frequency heating device or an air oven is preferable. Examples of the aqueous type surface treatment agent include aqueous urethanes such as aliphatic and aromatic ones. The coating amount of the aqueous type surface treatment agent is preferably such that the thickness of the formed film is 0.1 to 100 μm, more preferably 1 to 5 μm.
The thickness is appropriately selected so as to be 0 μm. The formed film has excellent adhesion to the surface of the weather strip.

The shape of the weather strip may be any of conventionally known shapes, for example, JP-A-4-368223, JP-A-11-48788, and JP-A-11-7.
One having the shape described in Japanese Patent No. 0544 or the like can be mentioned.

[0059]

EXAMPLES The present invention will be described below in detail with reference to examples, but it should be understood that the present invention is not construed as being limited to the examples.

(Olefin copolymer having functional group)
(Production of (A)) Production Example 1 Hexane 20 was placed in a 2 L separable flask purged with nitrogen.
00 mL and 5-methyl-5-carboxy-bicyclo
[2.2.1] 2-heptene 0.5 mol / L hex
77 mL of sun solution (5-methyl-5-carboxyl-bi
Cyclo [2.2.1] -2-heptene 39 mmol)
I put it. Then, while stirring the system, Al (iso-
Bu)_ThreeBy adding 47 mmol of
5-methyl-5-carboxy-bicyclo [2.2.
1] Maskin of carboxyl group in 2-heptene
Was performed. Then, 5-ethylidene-2 was added to this system.
2 ml of norbornene, and ethylene (supply amount: 5 L)
/ Min) / propylene (supply rate: 5 L / min) / water
(A supply amount: 0.3 L / min)
While feeding, as a polymerization catalyst, Al_Two(C_TwoH_Five)_ThreeCl_Three
Of a 0.81 mol / L hexane solution of 116 mL (Al_Two
(C _TwoH_Five)_ThreeCl_Three94 mmol) and then V
Cl_FourOf a 0.10 mol / L hexane solution in 24 mL (V
Cl_Four2.4 mmol) at 25 ° C. for 10 minutes.
Under the conditions, ethylene, propylene and 5-methyl-5-
Of carboxy-bicyclo [2.2.1] -2-heptene
A copolymerization reaction was performed.

705 mmol was added to the obtained copolymer solution.
Was removed by adding a butanol solution containing lactic acid and stirring for 10 minutes. Next, after adding 1 L of water to the copolymer solution and stirring for 10 minutes, only the copolymer solution (organic layer) is recovered, and the copolymer solution is washed three times with 1 L of water to obtain a residual solution. Lactic acid and the like were removed. Then, the solvent was removed by blowing steam into the copolymer solution. Then, the solid content is separated from the obtained slurry,
This was dried by a heating roll to obtain 28 g of a solid olefin copolymer (A1).

When the olefin copolymer (A1) was analyzed by infrared absorption spectroscopy, the content of structural units derived from ethylene was 64.0 mol%, and the content of structural units derived from propylene was 33%. 0.7 mol%,
5-methyl-5-carboxy-bicyclo [2.2.1]
The content ratio of structural units derived from -2-heptene is 1.1.
Mol%, the content of structural units derived from 5-ethylidene-2-norbornene was 1.2 mol%. Also, 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 2.2.
It was 5 dl / g.

Production Examples 2 to 5 Olefin copolymers (A2) to (A5) shown in Table 1 were produced in substantially the same manner as in Production Example 1.

COMPARATIVE PREPARATION EXAMPLES 1-2 In Preparation 1, except that 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was not copolymerized,
Comparative olefin copolymers (X1) and (X2) shown in Table 1 were produced in substantially the same manner as in Production Example 1.

[0065]

[Table 1]

Examples 1 to 5, Comparative Examples 1 and 2 The olefin copolymers (A1) to (A4), (X1) to (X1) produced in Production Examples 1 to 5 and Comparative Production Examples 1 and 2 described above.
2) 100 parts by weight, 150 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd .: Seast SO), 1 part by weight of stearic acid, and 50 parts by weight of process oil (trade name: FUKKOR 2050N manufactured by Fujikosan Co., Ltd.) Was kneaded for 180 seconds at a rotation speed of 60 rpm and 50 ° C. using a Labo Plastomill having a content of 250 mL to obtain seven types of compounds (1). Next, 5 parts by weight of a foam inhibitor (Inoue Lime Vesta PP), 5 parts by weight of zinc oxide, 1 part by weight of a vulcanization accelerator (tetramethylthiuram disulfide), and a vulcanization accelerator (mercaptobenzo) were added to each compound (1). 0.5 parts by weight of thiazole) and 1.5 parts by weight of sulfur were added, and kneaded with a 10-inch roll maintained at 50 ° C. for 5 minutes to obtain a compound (2). In Example 5, as the olefin copolymer,
Olefinic copolymer (A5) 10 produced in Production Example 5
Parts by weight and an ethylene / propylene / ENB copolymer (trade name: EP57, manufactured by JSR Corporation, ethylene content: 76.1)
100 parts by weight of a mixture consisting of 90% by weight (mol%, propylene content: 22.7 mol%, ENB content: 1.2 mol%, [η]: 2.23 dl / g) were used.

Each of the compounds (2) obtained above was extruded with a 2 mm-thick plate die using a rubber extruder, and then one surface was treated with a urethane aqueous type surface treating agent (trade name: Ucoat). UWS-145, manufactured by Sanyo Chemical Co., Ltd.) was applied, and vulcanization and curing of the surface treatment agent were simultaneously performed in hot air at 200 ° C. × 5 minutes to obtain a sample.
Using this sample, an adhesion test was performed by the following method.
The results are shown in Table 2. 16 more compound (2)
Press pressure 150kg by hot press heated to 0 ° C
Heating was performed at a pressure of f / cm ² for 30 minutes to obtain a vulcanized sheet. Using this vulcanized sheet as a test piece, a tensile test was performed by the following method. Table 2 shows the results. (1) Adhesion test-Peeling test: a small amount of Alon alpha was dropped on the surface of the surface treatment agent film, a tetron cloth was further placed on it and cured at room temperature, and a 180 degree tensile test was performed on the rubber surface and tetron (registered trademark) cloth. The strength was defined as the peel strength.・ Sliding test:
The adhesion between the vulcanized rubber layer and the film formed from the urethane-based surface treatment agent was evaluated by the number of times required until the rubber substrate was exposed when sliding on glass. (2) Tensile test According to JIS K 6301, tensile strength TB (M
Pa) and elongation at break EB (%) were measured.

[0068]

[Table 2]

From the results shown in Table 2, the urethane-based aqueous type surface treatment agent was applied to the surface of the compounded rubber molded article for weatherstrip containing the olefin-based copolymer (A) having a functional group. It is clear that the obtained vulcanized product has a film having excellent adhesion.

[0070]

According to the weather strip of the present invention, an olefin polymer is used as a material, and a film having excellent adhesion can be formed even when an aqueous type surface treatment agent is used. Sliding properties can be imparted.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 220/04 C08F 220/54 220/54 226/02 226/02 232/00 232/00 C08J 3/24 CESZ C08J 3/24 CES C08K 3/06 C08K 3/06 3/30 3/30 5/14 5/14 5/36 5/36 B60J 1/16 A (72) Inventor Minoru Tanaka Tsukiji, Chuo-ku, Tokyo No. 11-24, JSR Co., Ltd. (72) Inventor Fumio Tsutsumi 2-11-11, Tsukiji, Chuo-ku, Tokyo F-term in JSR Co., Ltd. 3D127 AA17 AA19 BB01 CB02 DE02 GG09 4F070 AA13 AA25 AA29 AA35 AA38 AC04 AC05 AC13 AC40 AC50 AC94 AE01 AE08 GA05 GA06 GC02 GC07 4J002 BB051 BB052 BB081 BB101 BJ001 DA046 DA116 DD006 EK036 EV046 EV146 EV166 FD146 GN00 4J100 AA02P AA03Q AA04Q AA07Q AA15AQA 2Q AB03Q AD03R AE03R AE04R AE13R AG04R AJ02R AM14R AM15R AM17R AN03R AN04R AR09R AR11R AR21S AR22S AS11S AU21S AU22S BA03R BA05R BA16R BA20R BA30R BA34R CA05 CA06 DA09 JA28

Claims (6)

[Claims] 1. (A) (a-1) a structural unit derived from ethylene, (a-2) a structural unit derived from an α-olefin having 3 to 10 carbon atoms, and (a-3) a functional unit containing no functional group. A structural unit derived from a saturated compound, and if necessary, (a-4)
Having a structural unit derived from a non-conjugated diene compound,
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.1 to
A weather strip obtained by vulcanizing an olefin-based copolymer having a functional group of 10 dl / g and (B) an olefin-based copolymer-containing rubber composition containing a vulcanizing agent and / or a crosslinking agent. 2. The olefin copolymer (A) having a functional group has a structural unit (a-1) of 5 to 90 mol%, a structural unit (a-2) of 5 to 50 mol%, and a structural unit of (A-
3) in an amount of 0.01 to 5 mol%, and the structural unit (a-4)
The weatherstrip according to claim 1, which has 0 to 10 mol%. 3. The functional group-containing unsaturated compound derived from the structural unit (a-3) is a compound represented by the following formula (1) and / or the following formula (2). Weather Strip. CH ₂ = CR ^1- (CH ₂ ) _n -X Formula (1) (In the formula (1), X is -OR ¹ , -COOH, -NH
R ¹ represents a functional group of —CONHR ¹ , wherein R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 6. ) (In the formula (2), R ² represents a hydrogen atom or a carbon atom having 1 to 10 carbon atoms.
Y ¹ , Y ² , and Y ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or —OR ¹ , —COOH, —NHR ¹ , or —CONH
Represents a functional group of R ^1, at least one of Y ^1, Y ^2, Y ³ is a functional group, and when two or more of Y ^1, Y ^2, Y ³ is a functional group, They may be acid anhydrides (-O- (CO) -O-) or imide groups (-CO-NH-CO-) formed by linking each other. R ¹ is
Hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and o is 0 to 2
And p is an integer of 0 to 5. ) 4. The functional group X in the formula (1) or at least one of Y ¹ , Y ² and Y ³ in the formula (2) is a —COOH group. ~
4. The weatherstrip according to any one of 3. 5. The weatherstrip according to claim 1, wherein the functional group-containing unsaturated compound derived from the structural unit (a-3) is a compound represented by the formula (2). 6. A functional group-containing olefin copolymer according to claim 1, (B) a vulcanizing agent and / or a crosslinking agent, and (C) a functional group-free olefin copolymer. A weather strip obtained from a rubber composition containing an ethylene / α-olefin copolymer.