JPH0476034A - Wiper blade rubber molding and its production - Google Patents

Abstract

PURPOSE:To obtain a wiper blade rubber molding excellent in environmental aging resistance and dynamic fatigue resistance and having a long service life by molding a higher alpha-olefin rubber comprising a higher alpha-olefin and a nonconjugated diene, and having a specified intrinsic viscosity and a specified iodine value and vulcanizing the molding. CONSTITUTION:A wiper blade rubber molding is obtained by molding a higher alpha-olefin copolymer rubber comprising a 6-12C higher alpha-olefin and a nonconjugated diene of the formula (wherein R<1> is 1-4C alkyl ; R<2> and R<3> are each II or 1-4C alkyl provided that both R<2> and R<3> cannot be simultaneously H), and having an intrinsic viscosity [eta] as measured in a decalin solvent at 135 deg.C of 1.0-10.0dl/g and an iodine value of 1-50, and vuncanizing the molding. As the nonconjugated diene, 7-methyl-1,6-octadiene can be desirably used.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a wiper blade rubber molded article and a method for manufacturing the same, and more particularly, to environmental agglomeration resistance (heat resistance, 1iiJ weatherability, 11iJ ozone resistance). The present invention relates to a wiper blade rubber molded product having excellent dynamic fatigue resistance and a long life, and a method for manufacturing the same.

Technical Background of the Invention Rubber products (wiper blade rubber molded bodies) used for wiper blades of vehicles such as automobiles, trains, aircraft, and ships are constantly exposed to sunlight, wind and rain, and therefore have excellent heat aging resistance. It is required to have weather resistance and ozone resistance.

Conventionally, the above-mentioned wiper blade rubber molded products have been made using natural rubber (NR), butadiene rubber (R) as raw materials.
Rubbers such as 3R) and chloroprene rubber (-CR) have been used.

However, in conjunction with the recent demand for maintenance-free wiper blade rubber molded bodies, there has been a demand for a longer lifespan of wiper blade rubber molded bodies.

Therefore, various attempts have been made to realize the use of ethylene-propylene rubber (EPI), which has excellent environmental aging resistance, in wiper blades.

However, conventional wiper blade rubber molded bodies using EPDM have a problem in that they are prone to fatigue and breakage under so-called dynamic conditions, where vibrations are particularly severe.

Therefore, there has been a desire for a wiper blade rubber molded body that has excellent environmental aging resistance, excellent dynamic fatigue resistance, and has a long life.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and is aimed at improving environmental aging resistance (heat aging resistance,
The purpose of the present invention is to provide a wiper blade rubber molded article that has excellent weather resistance, ozone resistance), excellent dynamic fatigue resistance, and a long life, and a method for manufacturing the same.

Summary of the Invention The wiper blade rubber molded article according to the present invention has a carbon number of 6.
~12 higher α-olefins, and the following general formula [I]
It is composed of a non-conjugated diene represented by
．． 0-10. It is characterized by being made of a vulcanized product of a higher α-olefin copolymer rubber having an iodine value of 1 to 50 and an iodine value of 1 to 50.

(In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are not both hydrogen atoms.) The method for manufacturing a wiper blade rubber molded article according to the present invention is characterized in that the above-mentioned high α-olefin copolymer rubber is molded and vulcanized.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the wiper blade rubber molded article and the manufacturing method thereof according to the present invention will be specifically explained.

High α-olefin copolymer rubber The high α-olefin copolymer rubber used in the present invention is composed of a high α-olefin and a non-conjugated diene.

The higher α-olefin used in the present invention has 6 carbon atoms.
-12 α-olefins, and specific examples thereof include hexene-11, butene-1, octene-1, nonene-1, Desen Publishing, undecene-1, dodecene-1, and the like. In the present invention, the above-mentioned higher α-olefins may be used alone or as a mixture of two or more. Among the above higher α-olefins, hexene-11 octene-1 and decene-1 are preferably used.

The km of the higher α-olefin constituting the higher α-olefin copolymer rubber used in the present invention is 70 to 99.
99 mol%, preferably in the range of 80 to 99.9 mol%.

The non-conjugated diene used in the present invention has the following general formula [1
] is a non-conjugated diene.

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, R2 and R
3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are never both hydrogen atoms. )-1- as mentioned above (specifically, 6-methyl-1,6-'Actane, 7-methyl-
1,6 octadiene, 6-ethyl, 6-octadiene, 6-broby-1,6-octadiene, 6-phthyl-1,6 octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,(;- Nonaneene, 6-ethyl-1
, 6-nonadiene, 7-ethyl-1,6-nonadiene,
6-methyl publication 213 decadiene, 7-methyl-1,6-
Examples include zocasien and 6-methyl-1,6-undecadiene.

In the present invention, the non-conjugated diene mentioned above may be used as the non-conjugated diene in the raw form at °C, or it may be used as a mixture of two or more types.

Of the above-mentioned non-conjugated dienes, 7-methyl and 6-octacyene are preferably used.

The iodine value of the higher α-olefin copolymer used in the present invention is 1 to 50, preferably [7 or 2 to '30,
More preferably, it is 4 to 2[-]. Generally, high-class α
If the iodine value of the -4 reflexine copolymer rubber becomes too high, the resulting rubber composition tends to have low elongation and become brittle. On the other hand, if the iodine value of the high-grade α-olefin polymer rubber becomes too small, the vulcanization rate of the resulting rubber composition becomes slow, making it impractical for practical use.

Intrinsic viscosity "η" of the higher α-olefin copolymer rubber used in the present invention measured in 35°C decalin solvent
is 1.0 to 10. (ldβ/, preferably 2.0 to
9. (ldΩ/g, more preferably 3.0 to 8.Od
It is Ω/g. ” - Intrinsic viscosity [η] is 10 dΩ/g
If it exceeds 100 dΩ/g, the resulting rubber composition tends to be difficult to load, while if the intrinsic viscosity [η] is less than 10 dΩ/g, the strength characteristics of the obtained rubber composition tend to decrease.

4, Q of the non-conjugated diene constituting the higher α-olefin copolymer rubber used in the present invention is n, 01 to 30
mol %, preferably in the range of 0.1 to 20 mol %.

, H:, the composition of the class α-olefin, in-based copolymer rubber is 1
Measured by 3C-NMR method.

The higher α-olefin type polymer used in the present invention can be produced by the J' method described below.

The higher α-olefin copolymer rubber used in the present invention has rj -i'E-F of the first Nofin polymerization catalyst,
By polymerizing higher (r-1st/), i/ and 11 conjugated diene, ?11 can be obtained.

-1-1' (The olefin polymerization catalyst used during polymerization consists of a solid titanium catalyst component [A], an organic aluminum I, a compound catalyst component [B], and a 1"li J'
f! It is formed from I, lj catalyst component [C].

FIG. 1 does not show an example of Solo Char 1 of the method for preparing a catalyst component for olefin polymerization used in the production of higher α-olefin type J (polymer rubber) in the present invention.

The first titanium catalyst component [A] is a highly 11-prone catalyst component which contains magnesium, titanium, halogen, and 2,11-isomers as essential components.

Such a solid titanium catalyst component [A] is a magnesium compound, a titanium compound, and an electron 1'i
, 'j are brought into contact with each other.

Examples of the titanium compound used in the preparation of the solid titanium catalyst component (A) include 4 represented by Ti(OR) titanium compounds with high valence. More specifically, Ticρ
, TiBr , TiI4 and other titanium halides Ti(OCH3)C4! 3, Ti(OC2H3)CΩ3, Ti(On-CH) CΩ3, Ti(OC2H5)Br3, Ti(Oiso C4H9)B C3! , +: and alkoxytitanium trihalonide T I (OCH3) 2 C, C! 2.Ti(OC2
H5),, CΩ2, Ti (○ll-C4H9) 2CfI2, T + (O
CR) B r 2 halogenated sialkoxytitanium.

T I (oc n ?, ) 3cΩ, Ti(OC
2H5) 3CD.

Ti (On-C4H9) 3CN.

Monohalogenated I-alkoxytitaniums such as Ti(OC2H5)sBr; Ti(OCH3)4, Ti(OC2H5)4, T+(On C4H9)i.

Examples include tetraalkoxytitanium such as Ti(Oiso-C4H9)4TI(0-2-ethylhexyl)4.

Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used in the preparation of the solid titanium catalyst component [A] include magnesium compounds that have reducing properties and magnesium compounds that do not have reducing properties.

Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include diethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, Examples include butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxychloride. Alkoxymagnesium halides such as magnesium, octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium,
isopropoxymagnesium, butoxymagnesium,
Alkoxymagnesiums such as 11-octoxymagnesium and 2-ethylhexoxymagnesium; Allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; Magnesium laurate;
Examples include magnesium carboxylates such as magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned magnesium compounds that exhibit reducing properties, or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol. All you have to do is contact it.

In addition to the above-mentioned magnesium compounds having reducing properties and non-reducing properties, magnesium compounds include complex compounds, composite compounds, or mixtures of the above-mentioned magnesium compounds with other metals, or other metal compounds. It's okay. Furthermore, a mixture of two or more of the above compounds may be used.

Among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Electric j' used for preparing solid titanium catalyst component [A]
f! ';'j-isomer and 12 (e, white')-carboxylic acid esters are preferred.
Specifically, examples include 1, a compound having the above-mentioned J (J) and VI rating.

\ -, COOR' R4/ ' to COOR2 In the above formula, R1 is a substituted or unsubstituted hydrocarbon)J
(, R2R5R6 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R3R4 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group. It is preferable that it is a hydrocarbon group.Also, R3 and R4 may be linked with H to form a cyclic structure. Examples include substituted hydrocarbon groups containing heterogenic r, such as C-0-(,--COOR,-COOHlOH,-3o
Substituted hydrocarbon groups having a structure such as 3H, -C-N-C--NH2 may be mentioned (1).

Among these, at least -h of RR2 or a diester derived from a dicarboxylic acid which is an alkyl group having 2 or more carbon atoms is preferred.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate,
Diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethyl malonate,
Diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diisobutylcyloethyl malonate, diethyl dinormal phthylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, Diisobutyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di2-ethylhexyl fumarate, diethyl itaconate, isobutyl itaconate, diisooctyl ntraconate, dimethyl citracconate, etc. aliphatic polycarboxylic acid esters such as diethyl 1,2-chlorohexanecarboxylate, diisophthyl 1,2-chlorohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, Monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethylisobutyl phthalate, mono-n-butyl phthalate, ethyl-n-phthalate, n-propyl phthalate, diisopropyl phthalate , di-butyl phthalate,
Isobutyl phthalate, hebutyl phthalate 1, -7
Di-2-ethylhexyl talate, didenyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, trimellitic acid ester, 3,4-furandicarboxylic acid, etc. Examples include esters derived from ring polycarphonic acids.

Other examples of polyhydric carbonic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, dielphthyl sebacate, 11-octyl sebacate, di-2-ethyl t\xyl sebacate,
Mention may be made of esters derived from long-chain dicarboxylic acids.

Among these polyhydric carbonic acid esters, compounds having an open circuit represented by the above-mentioned general formula are preferred;
More preferably, esters derived from phthalic acid, maleic acid, substituted malonic acid, and alcohols having 1 or more carbon atoms are preferred, and phthalic acid and alcohols having 2 or more carbon atoms are preferred.
! Particularly preferred are diesters obtained by reaction with -ru.

These polyvalent carboxylic acid esters do not necessarily need to be used as starting materials, and these polyvalent carboxylic acid esters can be derived in the process of preparing the solid titanium catalyst component [A]. A polyhydric carboxylic acid ester may be produced in the preparation step of the solid titanium catalyst component [A] using a compound that can be used.

Electron donors other than polyhydric carboxylic acids that can be used when preparing the solid titanium catalyst [A] include alcohols, amines, amides, ethers, ketones, and J.Kols, phosphines, stipines, arsines, phosphoramides, esters,
Thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (
Examples include organosilicon compounds such as (aryloxy)silanes, organic acids, and amides and salts of metals belonging to Groups 1 to 2 of the periodic table.

The solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metal magnesium), an electron donor, and a titanium compound into contact with each other. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron conjugate can be employed. Note that the above components include, for example, silicon,
The contact may be made in the presence of other reaction reagents such as phosphorus and aluminum.

Several examples of methods for producing these solid titanium catalyst components [A] will be briefly described below.

(1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like.

Moreover, when reacting as described above, a solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron polymer and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. Note that in this method, the above electron donor is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid titanium complex is precipitated by reacting a liquid titanium compound in the presence of an electron donor.

(3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound.

(4) A method in which the reaction product obtained in (1,) or (2) is further reacted with an electron donor and a titanium compound.

(5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Also,
7 A complex compound consisting of a magnesium compound or a magnesium compound and an electron donor may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Note that in this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon.

(7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

”-Solid titanium catalyst components listed in (1) to (8) [A
] Among the preparation methods, preferred are a method using liquid titanium halide during catalyst preparation, a method using a halogenated hydrocarbon after using a titanium compound, or a method using a halogenated hydrocarbon when using a titanium compound.

Used when preparing solid titanium catalyst component [A]
-4 The amount of each component used varies depending on the preparation method and cannot be specified as -111, but for example, the amount of -11 electrons per mol of the magnesium compound is approximately 0.01 to 5.
mol, preferably I-2< is an amount of 0.05 to 2 mol, and the titanated 6th grade is about 0.01 to 500 mol, preferably 0.05
It is used in an amount of ~300 mol.

The solid titanium catalyst component [A] prepared in this way contains magnesium, titanium, halogen and electron di,
Contains Ij form as an essential component.

In this solid titanium catalyst component [A], the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 10.
0, the electronic IF knee! J-body/Titanium (molar ratio)
is about 0.1 to 10, preferably about 0.2 to about 6,
Magnesium/Titanium (original rJ1.) C approx. 1. -10
0, &J' Mat, < Ha about 2-5 (preferably 1 Te).

The second solid titanium catalyst component [A] contains magnesium halide with a small crystal size compared to commercially available magnesium halides, and usually has a specific surface area of about 50 m2.
/ p; 2, preferably about 60-1, OOOi/
g, more preferably about 100 to ROOrrr/g. Since the solid titanium catalyst component [A] is composed of the above-mentioned components to form a catalyst component, the composition of the solid titanium catalyst component [A] is not substantially changed by hexane washing.

Such a solid titanium catalyst component [A] can be used as a medium or diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition,
When a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than that of the two series.

Regarding the preparation method of such a highly active titanium catalyst component, for example, JP-A-50-108385 and JP-A-50-108385.
-126590, No. 51-20297, No. 5128189, No. 5+-64588, No. 51-92885, No. 51-1.3 B 625
No. 52-87489, No. 52-1.00
No. 596, No. 52-1476H, No. 52-1
No. 04593, No. 53-2580, No. 53-
No. 40093, No. 53-40094, No. 53
-43094, No. 55-135102, No. 55-135103, No. 55-152710, No. 1iil 56-81.1, No. 5B-119
08 Publication, 56-18 [106 Publication, 58-8
Publication No. 3001'i, Publication No. 58-138705, Publication No. 58-13870 Publication Ei, Publication No. 58-138707
No. 58-188708, No. 58IH70
! Publication No. 1, Publication No. 58-138710, Publication No. 581
No. 38715, No. 60-23404, No. 61
-21109 Publication, Publication No. 61-87802, Publication No. 6
No. 1-37803, disclosed in Nato.

The aluminum compound catalyst component [B] contains at least one A, c! - Compounds that support carbon bonds can be used. Such compounds include, for example, Good.
<3, q is a number such that []≦q′3, and m+n
+p→-q=3), (ii)-M'Af! Examples include complex algylation products of Group 1 metals represented by R1 (wherein Ml is Li, Na, and R is the same as above) and aluminum.

Examples of the aluminum compounds belonging to the above (i) include the following compounds.

-Slaughter RAρ (OR2) m 3-m (in the formula
R1 and R2 are the same as above. “11 is preferably 1.
5≦m≦3), General formula RAρX3-m (In the formula, R1 is the same as above. RA, 17H3-0 (In the formula, R1 is the same as above. m is preferably 2≦m<3
), (wherein R1 and R2 are the same as above.
+ q = 3).

More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. a partially alkoxylated alkyl aluminum having an average composition of 0.5 expressed as ethyl aluminum sesquiethoxide, butyl aluminum sesquiethoxide, alkyla 2 fluminium sesqui alkoxide, R12,5A(1(OR), etc.); Dialkyl aluminum halides such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquipromide; ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum Partially halogenated alkyl aluminum such as alkyl aluminum cybarides such as dibromide; dialkyl aluminum hydrides such as diethylaluminum hydride, dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride , etc.; Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxypromide, etc.

Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H5)2A, 1! OAρ
(C2R5)2, (C4H9)2A, Q OAρ (C
4H9)2, methylaluminoxane, and the like.

Examples of compounds belonging to (ii) above include LiAΩ (
Examples include C2H5)4, LiAΩ(C7H15)4, and the like.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined.

As the electron donor catalyst component [C], oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Nitrogen-containing electron donors such as , ammonia, amines, nitriles, isocyanates, or polyhydric carboxylic acid esters as described above can be used. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol Alcohols having 1 to 18 carbon atoms such as phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol, cumylfuconol, naphthol, etc.; Getones with 6 to 2 carbon atoms [1 phenols; 3 to 5 carbon atoms such as acetone, methyl ethyl ketone, methyl isophyl getone, acetophenone, amphenone, and benzoquinone] acetaldehyde diraldehyde, heres 7 'ruthehyde, )・rualdehyde, -J-7 aldehyde angle with 2 to 15 carbon atoms such as toaldehyde, methyl oxate, acid resistant methyl, edyl 11'l acid, vinyl he'1 acid, n'1 acid Polypropylene, acid-resistant octyl, acid-resistant cyclohexyl, ethyl propionate, methyl butyrate, ethyl l-ljr'jl acid, methyl chlorobutyrate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexylcarboxylate, methyl benzoate , ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, li, 'J. 75
cyclohexyl acid, phenyl benzoate, pencil benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-nhexyl cyclohexenecarboxylate , diethyl nazic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-11-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. Number 2 to 30 white acid esters acetyl chloride, benzoyl chloride, toluic acid chloride,
Acid halides with 2 to 5 carbon atoms such as anisyl chloride; ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl needle, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acetic acid amide, benzoic acid amide,
Acid amide F such as toluic acid amide: amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aninone, pyridine, picoline, tetramethylenecyamine; acetonitrile'-32 tolylic acid, Anhydride = 7 Acid anhydrides such as talic acid and benzoic anhydride are used.

In addition, heavy weight (Jl, 'j catalyst component [C], te, 1
・An organosilicon compound represented by the general formula [1] as shown below can also be used.

RSi(OR') 4.1...
[I]+1 In the L formula, R and R′ are hydrocarbon groups, and 0>I]<
Specific examples of the organometallic compounds represented by the general formula [1] as shown in the following are trimethylmethoxine, lanyldimethoxysilane, diisopropyldimethoxysilane, and [-phthylmethyldimethoxysilane]. Toquinsilane, butylmethylshedoxinran,
E-amylmethyljethoxysilane, Schiff-onyldimethoxysilane, phenylmethyldimethoxysilane, 0-tolylcimethoxysilane, bisml-lylcimethoxysilane, bispl-lyldimethoxysilane, bis1]- Tolyljethoxysilanyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohequinylmethyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilanedecyltriethoxysilane, Decyltriethoxine, lpropyltrimethoxysilane, silane, butyltriethoxysilane, ethoxysilane, gamma-aminopropyltriethoxysilane, ethyltriisopropoquine, pinyltributoquine, chlorohexyltrimethoxysilane, Toxinlan, cyclohexyltriethoxinelan, 2-norbornanetriethquinsilane'3 4 bornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(at 1yloxy)silane, vinyltris(β- methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, of which ethyltriethoxysilane Luthrie I xysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane phenyldimethoxy Silane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-1-lylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane diphenyljethoxysilane are preferred.

Further, as the 17-electron catalyst component [C], an organosilicon compound represented by the following general formula [n] can also be used.

S+R R (OR”), 12 m 3-m “”■] [R1 in the formula
is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, R3 is a hydrocarbon group, and m
is O≦m≦2. ] In the above formula [II], R+ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R1
In addition to the cyclopentyl group, examples thereof include cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

Further, in formula [n], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group exemplified as R1 and a cyclopentyl group having an alkyl group can be similarly mentioned.

Further, in formula [11], R3 is a hydrocarbon group,
Examples of R3 include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

Among these, R1 is a cyclopentyl group, and R2
It is preferred to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimeI-xysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, pentyl ethoxysilantyl methoxysilane, Examples include monoalkoxysilanes such as cyclopentyl ethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferred.

The olefin polymerization catalyst used in the production of high-grade α-olefin copolymer rubber consists of the solid titanium catalyst component [A] as described above, the organoaluminum compound catalyst component [B], and the electron donor [C ], and this olefin polymerization catalyst is used to polymerize a higher α-olefin and a non-conjugated diene. After preliminary polymerization, higher α-olefins and non-conjugated dienes can be polymerized (main polymerization) using this catalyst. per gram of olefin polymerization catalyst during prepolymerization,
(), 1-500 g, preferably 0.3-30 C1
g, particularly preferably 1 to 100 g, of α-olefin or higher α-olefin to be pre-Kt polymerized.

In p-preparation polymerization, it is possible to use a catalyst having an i't:+ concentration considerably higher than the catalyst concentration in the system in main polymerization.

The concentration of the solid titanium catalyst component [A] in the pre-polymerization is usually 0.01 to 200 mmol, preferably about 0.1 to 1.00 mmol in terms of titanium atoms per 1 Ω of the inert hydrocarbon medium described below mmol, particularly preferably 1
It is within the range of ~5 [] mmol.

The amount of aluminum catalyst component [B] in unit A is 01 to 500 g per g of solid titanium catalyst component [A], preferably 0.6 g.
The amount may be such that 3 to 300 g of polymer is produced, and the amount of titanium raw material r1 mole in the solid titanium catalyst component [A] is good.
The amount is usually from 0.1 to 3 to 100 mol, preferably from about 0.5 to 50 mol, particularly preferably from 1 to 20 mol.

The electron-reactive catalyst component [C] is a solid titanium catalyst component [
A, per mole of titanium atoms in] 0.1 to 50 moles,
Preferably 0.5 to 30 mol, particularly preferably 1 to 1
It is used in an amount of 0 mol.

Prepolymerization involves adding an olefin or higher α-olefin and the above catalyst components to a non-liq hydrocarbon medium,
It is preferable to carry out the reaction under mild conditions.

Examples of the inert hydrocarbon medium used at this time include propane, phthane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as cyclobenzene, cyclohexane, and methylcyclopentane. Sword scent of aliphatic hydrocarbons such as benzene, toluene, and xylene,! V.A.
Mention may be made of hydrocarbons such as ethylene chloride, hydrocarbons such as chlorobenzene, or mixtures thereof. It is preferable to use these non-talking hydrocarbon media, especially aliphatic hydrocarbons. Note that prepolymerization can also be carried out using the olefin or higher α-olefin itself as a solvent; Prepolymerization can also be carried out in the absence of a solvent.

The higher α-olefin used in the prepolymerization may be the same as or different from the higher α-olefin used in the wood cutting process described below.

]' (The reaction temperature during imm association is usually -20 to +
1. (,10°C, preferably 20 to +80
C, more preferably in the range of 0 to -1-400C.

In the polymerization, a molecular weight regulator such as hydrogen can also be used. Intrinsic viscosity of coalescence [η,
About 0.2C] Ω/g or more -1-1 preferably about C'1.5
It is desirable to use the amount such that ~1C) dR/g.

As mentioned above, in the 1'f-prepolymerization, the solid titanium catalyst component [A] is about 0.1 to 500 g per Ig, preferably about 0.3 to 300 g, particularly preferably 1 to 1,0 g.
This is carried out to produce a polymer of Og. F riii
If the polymerization amount is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously.

into an olefin polymerization catalyst as described above]' fii
ii polymerization to obtain the solid titanium catalyst component [A
], the presence F of an olefin polymerization catalyst formed from aluminum a, catalyst component [B], and electron J-i catalyst component [C], and the presence of a higher α-olefin and a non-conjugated diene. Copolymerization (main polymerization).

In the case of polymerization (main polymerization) of higher α-olefin and non-conjugated diene, in addition to the catalyst for olefin polymerization,
The same organic aluminum compound catalyst component (7) as the a-organic aluminum compound catalyst component [B] used in producing the olefin polymerization catalyst can also be used. JJ with
During the polymerization (main polymerization), the same electron donor catalyst component [C] used in the production of the olefin polymerization catalyst may be used as the donor catalyst component 7. Note that the organoaluminum compound and electron donor used in the copolymerization (main polymerization) of higher α-olefin and nonconjugated diene are not necessarily used in preparing the above-mentioned catalyst for olefin polymerization. The organoaluminum compound and electron donor need not be the same.

Copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene is usually carried out in a liquid phase.

In the copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, the solid titanium catalyst component [A] has a polymerization volume of 1
It is usually used in an amount of about 01001 to about 1.0 mmol, preferably about 0.005 to 0.1 mmol, calculated as titanium atoms per Ω. In addition, the organoaluminum compound catalyst component [B] usually has about 1 to 2000 moles of metal atoms in the organoaluminum compound catalyst component [B] per 1' mole of titanium atoms in the solid titanium catalyst component [A]. Preferably, the amount used is about 5 to 500 moles. Furthermore, per mole of metal atom in the organic aluminilla 11 compound catalyst component [B], the electron donor catalyst component [C]
Usually about 0.001 to 10 mol, preferably about 0.01
2 mol, particularly preferably about 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer rubber can be adjusted.

The polymerization temperature of higher α-olefin and non-conjugated diene is usually about 20 to 200°C, preferably about 40 to 100°C.
The pressure is usually set at normal pressure to 100 kg/cm, preferably normal pressure to 50 kg/cm. In the copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, the polymerization can be carried out by a batch method, a semi-continuous method, or a continuous method. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The wiper blade rubber molded article according to the present invention is composed of a vulcanized product of the above-mentioned higher α-olefin polymer rubber, but it also contains auxiliary agents used in the vulcanization reaction, such as metal activators, A compound having an oxynotylene structure or a scorch inhibitor may be polymerized. Furthermore, when the wiper blade rubber molded article according to the present invention contains additives such as rubber reinforcing agents, fillers, softeners, anti-aging agents, and additives, the properties as a wiper blade rubber molded article can be improved. further improves. Therefore, in the present invention, it is preferable to use the above additives.

Method for Manufacturing Wiper Blade Rubber Molded Body The wiper blade rubber molded body according to the present invention is preferably manufactured, for example, by the following method.

That is, the wiper blade rubber molded article according to the present invention is obtained by molding and vulcanizing the high-grade α-olefin copolymer rubber as described above.

Vulcanization is carried out by adding a vulcanizing agent to the high-grade α-olefin copolymer rubber, but it is preferable to add the vulcanizing agent before molding.

Further, as a method of vulcanizing the high-grade α-olefin copolymer rubber, sulfur vulcanization and organic peroxide vulcanization are effective.

Specifically, sulfur compounds used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide,
Examples include tetramethylthiuram disulfide and selenium dimethyldithiocarbamate. Among them, sulfur is preferably used. The sulfur compound is 0.1 to 1 part by weight per 100 parts by weight of the higher α-olefin copolymer rubber.
It is used in an amount of 0 parts by weight, preferably 0.5 to 5 parts by weight.

Further, when a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specifically, the vulcanization accelerator includes N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-
Benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiacylsulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6
- dinityl-4-morphotsunotio)benzothiazole,
Dibendithiane disulf, thiazole compounds such as itonato, diphenylguanidine, triphenylquanidine, diorthotolylquanisine, orthotolyl high quanitine, quanidine compounds such as Schiff J Nilquanisine panotalate: Acetaldehyde aniline reactants, phthylaldehyde aniline condensates, hekylymethyonetetramine, acetaldehyde ammoniadehyde-ammonia compounds, imitasoline compounds such as 2-merkabutimitazoline; thiocarhanylyl-1-
, diethylthiourea, dibutylthiourea, trimethylthiourea 7', thiuram-based compounds such as thiorthotolylthiourea, ditramethylthiuram monosulfite,
Thiuram compounds such as tetramethylthiuram disulfide, tetraphthylthiuram disulfide, and pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-buty-4-fludithiocarbamate, and ethyl phenyl dithiocarbamate. dithioate compounds such as zinc acid, zinc butylphenyldithiononorbamate, sthorium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, →notate compounds such as zinc dibutylgysanthate These vulcanization agents (JFL) can be used to prepare high grade (r-olefin copolymer rubber 10 (1
0, 1 to 20 parts by weight, preferably 0 to 1 part by weight
It is used in an amount of 2 to 10 parts by weight.

Specifically, peroxide-based vulcanizing agents used in organic peroxide vulcanization include dicumyl peroxide, 2,
5-dimethyl-2,5-di(tert-butylperoxy)hexadi, 2,5-dimethyl-2,5-di(benzoylperoxy)hexadi, 2,5-dimethyl-2.
5-di(LerL-butylperoxy)hexyne 3,
G t. cr L-butyl peroxide, theta
Examples include rt-butylberroquine-3.3.5-1-limethylcyclohexane and tcrt-butyl hydroperoxide. Among them, dicumyl peroxide, di-terl-butyl peroxide, di-terl-butyl peroxide,
L-butylperoxy-L3.5-l-limethylchlorohexane is preferably used.

In this J6 Ming, the above r1 peroxide-based vulcanizing agent is a high-grade α-olefin-based Jl (, Cff composite rubber 100
For g, suitable sound 3X i O ~ 5X10” moles,
Preferably 1×1n to 3×1 [12 moles, 1
Used in combination or in combination.

In the present invention, when a 6-unit peroxide is used as a vulcanizing agent, it is desirable to use a vulcanizing aid in combination. Examples of vulcanization aids include sulfur, quinonedioquine compounds such as p-quinonedioquine, methacrylate-1 compounds such as polyethylene glycol methacrylate-1, and arylphthale-1, 1-j arylphthale-1, Examples include allyl compounds such as, maleimide compounds, divinylbenzene, and the like. Such a vulcanization aid is used in an amount of 0.5 to 2 mol per 1 mol of the peroxide vulcanizing agent used.
Preferably, they are used in approximately equimolar proportions.

4. In addition, in manufacturing the wiper blade rubber molded article according to the present invention, the following vulcanization aid is further added to a high grade α
- It is preferable to add the above-mentioned vulcanizing agent (J4) to the olefin copolymer rubber at the same time.

Examples of vulcanization aids that are preferably used in combination with the vulcanizing agent include metal activators, compounds having an oxyethylene structure, and scorch preventive agents.

Specific examples of the metal activator include magnesium oxide, zinc white, zinc carbonate, higher fatty acid zinc, button activator, lizard, and calcium oxide. These metal activators are preferably used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber.

Further, in order to deal with various rubber additive processes, it is desirable to add a compound having an oxyethylene structure and a scorch preventive agent.

Specific examples of the compound having an oxyethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol. These compounds are usually used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 1.00 parts by weight of the high α-olefin copolymer rubber.

As the scorch inhibitor, a known scorch inhibitor can be used, and specific examples include maleic anhydride and salicylic acid. The above-mentioned scorch inhibitor is usually a high α-olefin copolymer rubber 10
0.2 to 5 parts by weight, preferably 0.3 parts by weight
It is used in a proportion of ~3 parts by weight.

The wiper blade rubber molded article according to the present invention has better properties as a wiper blade rubber molded article when it contains rubber reinforcing agents, fillers, softeners, anti-aging agents, processing aids, and the like. These additives are preferably mixed into the higher α-olefin copolymer rubber at an appropriate time before or after vulcanization.

Rubber reinforcing agents used in conjunction with vulcanizing agents, etc.
Specifically, SRF, GPE, FEF.

Examples include various carbon blacks such as MAF, HAF, ISAF, 5AFSFT, and MT, and finely divided silicic acid.

Specifically, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used as the filler.

These reinforcing agents and fillers are usually used in an amount of 20 parts by weight per 100 parts by weight of the higher α-olefin copolymer rubber.
It is blended in an amount of 0 parts by weight or less, preferably 150 parts by weight or less.

Specifically, softeners include process oil, lubricating oil, paraffin, liquid paraffin, and petroleum asphalt!・、
Petroleum-based substances such as vaseline, coal tar, coal tar such as coal tar pitch, fatty oils such as castor oil, linseed oil, rapeseed oil, and coconut oil, tall oil, sub, beeswax,
Waxes such as carnauba wax and lanolin, ricinoleic acid,
Fatty acids or their metal salts such as palmitic acid, barium stearate, calcium stearate, petroleum resins, synthetic polymer substances such as acidic polypropylene, coumaron indene resins, dioctyl phthalate-1, dioctyl adipe-1, Examples include ester plasticizers such as dioctyl sebaque-1, microcrystalline wax, sub(factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, and the like.

These softeners are generally appropriately blended in an amount of 100 parts by weight or less, preferably 70 parts by weight or less, based on 100 parts by weight of the higher α-olefin type J (polymer rubber).

Further, by using an anti-aging agent, it is possible to extend the material life of the wiper blade rubber molded article according to the present invention. This is the same as in the case of ordinary rubber. Specifically, the anti-aging agents used in this case include:
Aromatic secondary amine stabilizers such as phenylnaphthylamine, N,N'-di-2-naphthylphenylenediamine, dibutylhydroxytoluene, tetrakis[methylene (3
, 5-di-t-butyl-4-hydroxy)hydrocinnamate, phenolic stabilizers such as comethane, bis[2-methyl 4-(3-n-alkylthiopropionyloxy)
A thioether stabilizer such as -5-t-butylphenyl] sulfide, a dithiocarbamate stabilizer such as nickel dibutyldithiocarbamate, etc. may be blended alone or in combination of two or more.

Such anti-aging agent is usually used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the high-grade α-olefin copolymer rubber.
It is preferably used in a proportion of 0.65 to 3 parts by weight.

As processing aids, ordinary rubber additives 11.1. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, esters of the above acids, Examples include salts thereof and esters thereof.

These processing aids are generally used in an amount of about 10 parts by weight or less, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber.

In addition, in the present invention, in the i11 composition for the wiper plate comb molded article, within the range not impairing the object of the present invention,
Heat input rubber, diene rubber such as SBR, IR, BR, E
Other types of rubber such as PDM f, i can also be blended.

The wiper flade rubber molded article according to the present invention can be produced by, for example, preparing a rubber compound and molding it using the following method. I can do one thing.

That is, 1)! The primary α-olefin polymer rubber and necessary additives such as reinforcing agents, fillers, and softeners are mixed using a mixer such as a Hanbury mixer at approximately 80 to 100 ml.
．． After kneading at a temperature of 70°C for about 3 to 10 minutes, the vulcanizing agent and vulcanization aid are further mixed using rolls such as oven rolls, and the mixture is kneaded at a roll temperature of 40 to 80°C for about 5 to 30 minutes. The rubber compound is kneaded and fractionated to prepare a rubber compound in the form of a ribbon or sheet.

Alternatively, the high grade (l-olefin copolymer rubber and the above additives may be directly fed into an extruder heated to approximately 80 to 100 °C, and the residence time may be approximately 0.5 to 5 minutes. It is also possible to prepare rubber compounds in the form of pellets or pellets.

Next, the rubber compound prepared as described above is generally molded and processed using a press molding machine, a transfer molding machine, an injection molding machine, etc. to obtain a wiper blade rubber molded product. .

Furthermore, even if the wiper blade rubber molded body is not manufactured using the rubber compounds mentioned above, the rubber compounds that have been used in the past may also be used.
It is also possible to create a wiper blade rubber molded body with a long life by combining materials and bonding.

In addition, when manufacturing a wiper blade rubber molded body, for example, the surface of the wiper blade rubber molded body may be chlorinated, brominated, or fluorinated, or coated with a thin film of polyethylene or the like, or the surface of the wiper blade rubber molded body may be coated with a thin film of polyethylene or the like. It is also possible to apply treatments such as flocking short fibers to reduce the coefficient of friction and make products with even higher performance.

Effects of the Invention Since the wiper blade rubber molded article according to the present invention is made of tM from a vulcanizate of a specific high-grade α-olefin copolymer rubber, it has excellent environmental aging resistance (heat aging resistance, weather resistance,
It has excellent ozone resistance) and dynamic fatigue resistance.
It has the effect of having a long lifespan.

Moreover, according to the manufacturing method according to the present invention, a wiper flade rubber molded article having the above-mentioned effects can be obtained.

(The following is a blank space) The present invention will now be described with reference to Examples, but the present invention is not limited to these Examples.

Examples] (Preparation of solid titanium catalyst component) Anhydrous magnesium chloride 5.2 g, decane 442 m
1 and 390.6 g of 2-ethylhexyl alcohol] was heated at 30°C for 2 hours to form a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and further 1.3 g of phthalic anhydride was added at 1.300°C. The phthalic anhydride was dissolved in this homogeneous solution by stirring and mixing for a period of time. In this way? After cooling the homogeneous solution to room temperature, 75 ml of this homogeneous solution was heated to 20 ml of titanium tetrachloride (
, ) ml over 1 hour. After charging, the temperature of this mixture was increased to 110' over 4 hours.
When the temperature reached 1100C, 5.22g of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours without stirring. After 2 hours of reaction time, the solid part was collected by hot filtration, and this solid part was suspended in 275 ml of titanium tetrachloride (after stirring, it was stirred for 2 hours at 110°C).
The heating reaction was carried out for a period of time. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component prepared by the above procedure was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component thus obtained was 2.2% by weight of titanium, 58.1% by weight of chlorine, 19.2% by weight of magnesium, and 1.10.7% by weight of diisobutylphthale.

(Polymerization) Add 1 or 4 ounces of decane to a 5'00 m1 polymerization vessel equipped with a stirring blade.
2 ml octene-1 to 100 ml 1,7-methyl-1
, 6-octadiene (8 ml) was charged. The temperature of this solution was raised to 50°C, and hydrogen and nitrogen were each added at 10.1°C per hour. , 5 (l. After heating to 50'C, 0.625 mmol of triisobutylaluminum, 0.0 mmol of trimethylethoxysilane, calculated as 0.21 mmol of trimethylethoxysilane). Polymerization was started by charging 25 mmol of □ solid titanium catalyst component. After polymerization was carried out at 50°C for 30 minutes, a small amount of isobutyl alcohol was added to stop the polymerization, and the polymerization solution was poured into a large amount of methanol. The copolymer was then released by tIT.

Next, after collecting the copolymer 17 released, it was dried under reduced pressure at 120°C overnight to obtain 15.1 g of octene-1.7.
-Methyl-1,6-octadiene copolymer was obtained.

The intrinsic viscosity [η] of the obtained copolymer measured in decalin at 135°C was 3. 'Odn/g, and the iodine value (1
v) is 20, octene-l and 7-methyl-1.6
-octadiene (octene-1/7-methyl-1,6-octadiene) was 91/9.

The above polymerization conditions are shown in Table 1.

Vulcanized rubber test pieces were prepared according to the following procedure and subjected to the following tests.

First, a formulation was prepared using an 8-inch oven roll (manufactured by Nippo Roll Co., Ltd.) according to the formulation shown in Table 2.

there were.

Table 2 Sulfur vulcanization accelerator A (1,3 0,5 octene-1,7-methyl-1,6-octadiene copolymer rubber zinc stearate 1) I SAF carbon 2) +00.0 3.0 50.0 1) Product name Tsukusera M Manufactured by Iriuchi Shinko Chemical Industry ■ 2) Product name Tsukusera TT Manufactured by Iriuchi Shinko Chemical Industry ■ 1) Product name Zinc White No. 1 2) Product name Asahi #80 Manufactured by Sakai Chemical Industry ■ Asahi Carbon ■ Preparation Subsequently, a vulcanizing agent was added to the above formulation according to the formulation shown in Table 3. The kneading time was 3 minutes, and the roll surface temperature was 50°C/60°C (front roll/back roll).
It was divided into mm.

Subsequently, a press molding machine (a 150-t press molding machine for rubber manufactured by Kotaki Co., Ltd.) was used to prepare a 2-thick vulcanized rubber sheet and a test piece for a bending test from this separated sheet.

The pressing conditions were 160°C for 30 minutes.

Using the vulcanized rubber sheets and bending test specimens obtained as described above, their normal physical properties, heat aging resistance, weather resistance, ozone resistance, and dynamic fatigue resistance were evaluated according to the following test methods.

[Test method] (1) Normal physical properties (according to JIS K 6301) - Tensile strength (TB) - Elongation (EI3) - Spring hardness (HJISA) - Tear strength (TR) (2) Heat aging resistance (JIS (based on K 6301) 10
Tensile strength retention rate after aging at 0°C for 70 hours [A (T
), Elongation [AR (EB)] 7 B (3) Weather resistance (according to JIS B 7753) Sunshine weather meter Tensile strength retention after 1000 hours exposure [A (T, )], Elongation retention [ A (
EB) ] (4) Ozone resistance (JIS K [based on old i3) 40
℃, ozone concentration of 50 pphm, and the time until 20% elongation and rack generation was measured.

(5) Dynamic fatigue resistance (according to JIS K 63 inches) A bending test was conducted to measure the number of bends until a crack grew to 15 mm.

In addition, the number of bends was also measured in the same manner as above for a test piece that had been left in an air oven at 120° C. for 70 hours to age.

The results are shown in Table 6.

Example 2 A compounded rubber obtained in the same manner as in Example 1 was extrusion molded into the shape of a wiper blade, and vulcanized in steam at a pressure of 6.5 kg/cIIl for 30 minutes to obtain a wiper blade rubber molded body.

The strength, friction characteristics, and ozone resistance of the obtained wiper blade rubber molded body were evaluated according to the following test methods.

[Test Method] (1) Frictional Properties (a) Coefficient of Friction [11] A wiping durability test was conducted using a flat glass under the following conditions, and the coefficient of friction when dry was measured.

Wiper blade length 1. OCl mm Arm load 155g Stroke length + 150mm Speed + 45 ? 1 watering cycle (every minute) - 1 minute watering, 4 minutes city water (b) 1li
Coefficient of friction after weathering test [U] → No. 14111 for test j1 after 1000 hours of exposure using weather meter was determined in the same manner as method No.j in Section L (a).

(2) lIi, I Ozonability (according to JIS K 8801) Each wiper blade was held at 20% elongation in an atmosphere with a temperature of 4 CI''C and an ozone concentration of 50 ppbm, and the time until cracking occurred was measured.

The results are shown in Table 7.

Comparative Example 1 Ethylene zolobylene-5-ethylidene-2-norhornen (Kawane)
Ml 67 mol%, Mooney viscosity ML (121°C)
Example 1
In the same manner as above, a 2 mm thick vulcanized rubber band and a test piece for bending test were obtained and evaluated.

table PT-1 stearic acid zinc oxide FEF Car Pots Pluck 1) Paraffinic process oil triallylison annulate dicumyl peroxide 6.8 I) Product name 2) Product name Asahi #50 Made by Asahi Carphone ■ Diana Process Oil P W-9 (manufactured by Idemitsu Kosan ■) The results are shown in Table 6.

Comparative Example 2 The natural rubber, chlorobrene, and compounding agents were set to 2% as shown in Table 5, and the thickness was 2 in the same manner as in Example 1.
mm of vulcanized rubber seam I and bending test J°1? 1? , that one song in total? It was I.

Table 5 Natural rubber (+0 chlorobrene stearate zinc white F E F carbon black l) Baraf, in-based process oil 2) Trimethylolpropane), methacrylate 1, 3) Dicumyl peroxide, itomercabuthen, imitasol 2.2 .4-1-methyl-1,2 dihydroquinoline polymer 0.5 1) Product name Asahi #50 Manufactured by Asahi Carphone 91J 2
)Product Name Diana Process Oil I]W-9[11
+L made by Kokosan 3) Product name High Cross M Sei 1. Chemical results are shown in Table 6.

Example 3 Using the compounded rubber obtained in the same manner as in Example], two layers were extruded into the shape of a wiper blade covering the surface of the wiper plate 111 compounded rubber of Comparative Example 2, and the pressure was 6.5 kg.
/cn? The wiper blade rubber molded product was vulcanized for 30 minutes in steam, and the wiper blade rubber molded product was 111 and -1.1.611i was ij as in Example 2.

The results are shown in Table 7.

Comparative Example 3 A wiper blade rubber molded body was prepared using the compounded rubber obtained in the same manner as in Comparative Example] in the same manner as in Example 3. 111 The evaluation was conducted in the same manner as in Example 2.

The results are shown in Table 7.

Comparative Example 4 A wiper blade rubber molded article was obtained using the compounded rubber obtained in the same manner as in Comparative Example 2 in the same manner as in Example 3, and the evaluation thereof was performed in the same manner as in Example 2.

The results are shown in Table 7.

Example 4 In Example 1, octene-1,7-methyl-1,6
Instead of the octadiene copolymer rubber, as shown in Table 1 above, by changing the higher α-olefin and the polymerization conditions,
The process was carried out in the same manner as in Example 1, except that a hexene-door methyl 6-octadiene copolymer rubber obtained by copolymerization was used, to a thickness of 2 m+.
A vulcanized rubber sheet and a test piece for bending test were obtained and evaluated.

The results are shown in Table 6.

Examples In Example 1, octene-1,7-methyl-1,[
Copolymerization was carried out in the same manner as in Example 1, except that 4-methylpentene was added instead of the 1-octadiene copolymer rubber, as shown in Table 1 above. A vulcanized rubber sheet with a thickness of 2 mm and a test piece for bending test were prepared in exactly the same manner as in Example 1, except that 4-methylpenten-to-octenate 7-methyl-1,6-octadiene copolymer rubber was used. and evaluated it.

The results are shown in Table 6.

[Brief explanation of drawings]

FIG. 1 is a flowchart 1 diagram showing the process of preparing an olefin polymerization catalyst used in the production of a higher α-olefin copolymer rubber in the present invention. Patent applicant: Shogatsu Ishiura Kagaku Jogyo Co., Ltd.
Person Patent Attorney Shun Suzuki Column 7 of “3. Detailed Description of the Invention” of the specification subject to the partial amendment Correct as shown. (No changes to the content other than those stated in the column subject to amendment) 1゜Indication of the case 1990 Patent Application No. 1.90,989 Patent application filed July 191, 1990 (6) 2゜Name of the invention: Wiper blade rubber molded article and its manufacturing method 3゜Relationship with the amended case Patent applicant address: 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name
Mitsui Petrochemical Industries Co., Ltd. Representative: Shogo Takebayashi 4, Agent (zip code: 14t) Address: 3rd floor, Araku Building, 2-19-2 Nishigotanda, Parts Ward, Tokyo [Telephone: 03 (491) 31B1] Mekou Saku L

Claims (1)

[Scope of Claims] 1) Comprised of a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I], and having an intrinsic viscosity [η] measured in a decalin solvent at 135°C; ] is 1
．． It is in the range of 0 to 10.0 dl/g, and the iodine value is 1 to
A wiper blade rubber molded product characterized by being made of a vulcanized product of high-grade α-olefin copolymer rubber in the range of ^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.However, R^2 and R^3 are both hydrogen atoms. 2) It is composed of a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I], and has an intrinsic viscosity [η] measured in a decalin solvent at 135°C. 1
．． It is in the range of 0 to 10.0 dl/g, and the iodine value is 1 to
A method for producing a wiper blade rubber molded product characterized by molding and vulcanizing a high-grade α-olefin copolymer rubber in the range of 50; (In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, if R^2 and R^3 are both It is never a hydrogen atom.)