Crosslinkable rubber composition and use thereof

专利摘要:
The crosslinkable rubber composition of the present invention is crosslinkable at room temperature, has a gelation time at room temperature of 30 days or less, and the crosslinked rubber sheet obtained by crosslinking the composition at room temperature has a tensile elongation of 20% or more, There is no crack in the crosslinked rubber sheet even after treatment at 50 pphm ozone concentration for 96 hours. Specifically, the rubber composition comprises an ethylene /? - olefin / nonconjugated polyene random copolymer rubber comprising a specific terminal vinyl group-containing norbornene compound, a SiH group-containing compound having at least two SiH groups in one molecule, Based catalyst, a reaction inhibitor and / or a silane coupling agent. The sealing material, the potting material, the coating material and the adhesive of the present invention are the above-mentioned rubber composition. This rubber composition is capable of producing a crosslinked rubber molded article with high crosslinking speed at room temperature and efficiently producing a crosslinked rubber molded article (including a foamed article) having excellent weather resistance, ozone resistance, heat aging resistance and compression set resistance at low cost . Further, the present invention is suitably used for electric and electronic parts, transportation equipment, civil engineering and building materials, medical supplies and leisure goods.
公开号:KR20020025983A
申请号:KR1020027002148
申请日:2001-06-19
公开日:2002-04-04
发明作者:하구타다카시；아리노미츠나오；기구치요시하루；가와사키마사아키
申请人:나까니시 히로유끼；미쓰이 가가쿠 가부시키가이샤；
IPC主号:

专利说明:

Crosslinkable Rubber Composition and Use Thereof BACKGROUND OF THE INVENTION 1. Field of the Invention < RTI ID = 0.0 >
[2] Conventionally, curing materials have been used in sealing, coating, potting, and bonding objects in electrical and electronic components or transport, and in a variety of industries, such as civil engineering and construction, medical and leisure.
[3] As such a curing material, a curing material (composition) containing an organic polymer having a silicon-containing group capable of crosslinking by containing a hydroxyl group or a hydrolytic group bonded to each of the silicon atoms and forming a siloxane bond is known.
[4] However, since this curing material requires moisture at the time of curing, there is a problem that it takes a long time to cure.
[5] In order to solve the above problems, there has been developed a composition for crosslinking a polyorganosiloxane having an average of at least two vinyl groups in one molecule with an organohydrogensiloxane having two or more hydrogen atoms bonding to silicon atoms in one molecule. This composition can be used as a curing material because of its excellent weather resistance, water resistance and heat resistance. However, such a composition has a problem that its use is limited because it has a disadvantage that it is expensive, its adhesiveness is low, mold is easily generated, and gas permeability is unsatisfactory.
[6] Japanese Patent Application Laid-Open No. 4-185687 discloses a composition which solves the above problems. This composition comprises a compound having at least one alkenyl group in the molecule, a compound having at least two hydrosilyl groups in the molecule, a hydrosilylation catalyst, and a silane coupling agent. In the examples described in this publication, terminal allyl etherified polyoxypropylene, a polypropylene oxide having a hydrosilyl group, an allyl terminal polycaprolactam, a polycaprolactam having a cyclic hydrogen polysiloxane, an allyl terminal polyisoprene, a cyclic hydrogen And hydrogenated polyisoprene having a polysiloxane.
[7] However, the inventors of the present invention conducted tests in accordance with the examples described in this publication, and as a result, the curing time was shortened and the adhesiveness was improved, but the curing rate, weather resistance and heat aging resistance were still insufficient. In addition, it was required to improve the adhesiveness.
[8] Therefore, the inventors of the present invention have made extensive studies on the ethylene / - olefin / non-conjugated polyene random copolymer rubber composition and have found that the ethylene / - olefin / The rubber composition comprising the SiH group-containing compound (B) containing at least two SiH groups and optionally the catalyst (C), the reaction inhibitor (D), the silane coupling agent (E) and the plasticizer (F) It is possible to produce a crosslinked rubber molded article excellent in weatherability, ozone resistance, heat aging resistance and compression set resistance at a low cost, and has completed the present invention .
[9] Object of the invention
[10] It is an object of the present invention to solve the problems associated with the prior art as described above and to provide a crosslinked rubber molded article having a high crosslinking speed at room temperature and capable of efficiently producing a crosslinked rubber molded article and exhibiting excellent weatherability, ozone resistance, heat aging resistance and compression set resistance And a crosslinkable rubber composition capable of producing an excellent crosslinked rubber molded article at low cost. Another object of the present invention is to provide a crosslinkable rubber composition which is excellent in moldability and adhesiveness in addition to the above characteristics and is very suitable for sealing materials. It is another object of the present invention to provide a composition which is excellent in cure speed, weatherability, heat aging resistance, adhesion and the like, which are used for electric and electronic components or transport, and for use in other industries such as civil engineering, A sealing material, a potting material, a coating material, and an adhesive, which are excellent in adhesion to an inorganic material such as metal.
[11] DISCLOSURE OF INVENTION
[12] The first crosslinkable rubber composition of the present invention is a crosslinkable rubber composition at room temperature (25 DEG C), and has a gelation time at room temperature of 30 days or less, and the crosslinked rubber sheet obtained by crosslinking the composition at room temperature has a tensile elongation And a tensile rate of 500 mm / min) was 20% or more, and further treated for 96 hours in an ozone concentration of 50 pphm at 40 占 폚 according to the ozone deterioration test method prescribed in JIS K-5259, Have no characteristics.
[13] The gelation time is determined as follows. The frequency variation is measured using a scanning VNC (SVNC) (manufactured by Rapra Technology Ltd.). With the progress of the measurement, the frequency was increased, and when the frequency was stabilized, the frequency was set to 100%. The time at which the frequency was changed to 95% was defined as the gelation time (crosslinking time). The measurement temperature was room temperature, and the measurement was carried out in accordance with the following documents.
[14] (i) Operation manual (software version 2.2) of RAPRA Scanning vibrating needle type hardening tester (Injection VNC)
[15] (ii) Understanding of curing by RAPRA Scanning Vibration Erosion Curing Tester (Scanning VNC) (RTL / 2844)
[16] The second crosslinkable rubber composition according to the present invention comprises
[17] (A) an ethylene / - olefin / non-conjugated polyene random copolymer having a constitutional unit derived from at least one terminal vinyl group-containing norbornene compound represented by the following formula (I) or A rubber compound,
[18]
[19] Wherein n is an integer of 0 to 10,
[20] R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
[21] And R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
[22]
[23] Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
[24] (B) a SiH group-containing compound having at least two SiH groups in one molecule
[25] Respectively,
[26] And a gelation time at room temperature (25 DEG C) is 30 days or less.
[27] The second crosslinkable rubber composition according to the present invention comprises
[28] (A) an ethylene / - olefin / nonconjugated polyene random copolymer rubber,
[29] (B) a SiH group-containing compound having at least two SiH groups in one molecule,
[30] (C) Catalyst
[31] Or alternatively,
[32] (A) an ethylene / - olefin / nonconjugated polyene random copolymer rubber,
[33] (B) a SiH group-containing compound having at least two SiH groups in one molecule,
[34] (C) a catalyst,
[35] (D) the reaction inhibitor (D) and / or
[36] (E) Silane coupling agent
[37] .
[38] The second crosslinkable rubber composition may further contain 1 to 1,000 parts by weight of a plasticizer (F) based on 100 parts by weight of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A). In the case of using the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) having the following characteristics (i) to (v), it is preferable to use the plasticizer (F) in the above ratio.
[39] The ethylene / - olefin / non-conjugated polyene random copolymer rubber (A)
[40] (i) a molar ratio (ethylene / - olefin) of ethylene and an -olefin having 3 to 20 carbon atoms is 40/60 to 95/5,
[41] (ii) an iodine value of 0.5 to 50,
[42] (iii) an intrinsic viscosity [ ] of 0.01 to 2 dl / g as measured in decalin solution at 135 占 폚.
[43] In addition to the characteristics (i), (ii) and (iii), the copolymer rubber (A)
[44] (iv) a molecular weight distribution (Mw / Mn) measured by GPC of 3 to 100,
[45] (v) 100 g of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A) was subjected to press crosslinking at 170 ° C. for 10 minutes using 0.01 mol of dicumyl peroxide, (v) is preferably 0.5 x 10 ²⁰ chains / cm ³ or more.
[46] In addition to the properties (i), (i), (iii), (iv) and (v) above, the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A)
[47] (vi) obtained from a melt flow curve at 100 ℃, shearing stress 0.4 × 10 ⁶ a shear rate γ ₁ and shear stress corresponding to dyn / cm ² 2.4 × 10 ⁶ The ratio of a shear rate γ ₂ corresponding to dyn / cm ² ( ₂ / ₁ ) and the effective net cancellation density ( ) satisfy the following formula (III):
[48] _{^{0.04 × 10 -19 ≤Log (γ 2}} / γ 1) /ν≤0.20×10 -19 ---- (III)
[49] The ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) having the above properties (i) to (vi) can be obtained by using, for example, a catalyst containing the following compounds (H) and (I) , under the conditions of a polymerization temperature of 30 ~ 60 ℃, a polymerization pressure of 4 ~ 12kgf / cm ^2, a non-conjugated polyene and the molar ratio of the feed rate of ethylene (non-conjugated polyene / ethylene) 0.01 to 0.2, ethylene, α- olefin and the formula ( I) or (II).
[50] (H) VO (OR) _n X _{3-n wherein} R is a hydrocarbon group, X is a halogen atom and n is 0 or an integer of 1 to 3, or VX ₄ (X Is a halogen atom).
[51] (I) R ' _m AlX' _{3-m wherein} R 'is a hydrocarbon group, X' is a halogen atom, and m is 1 to 3.
[52] It is preferable that the content of the insoluble fraction after the extraction of the Soxlet (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) is 1% or less in the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A).
[53] As the catalyst (C), a platinum catalyst is preferably used.
[54] The second crosslinkable rubber composition according to the present invention is a crosslinkable rubber composition which can be crosslinked at room temperature. The crosslinked rubber sheet obtained by crosslinking the composition at room temperature has a gelation time at room temperature of 30 days or less and has a tensile elongation (JIS K-6251: A measurement temperature of 20 占 폚; a tensile speed of 500 mm / min) of 20% or more, and a crack-free property after being treated for 96 hours in an ozone concentration of 40 psi at 50 占 폚,
[55] It is particularly preferable that the crosslinking speed (t _c (90)) at 160 ° C is 15 minutes or less.
[56] The first and second crosslinkable rubber compositions preferably have an adhesive strength (measured according to JIS A 5758 (1986)) of 0.1 to 20 MPa, preferably 0.2 to 15 MPa, more preferably 0.5 to 10 MPa, It is preferably 1 to 5 MPa.
[57] The third crosslinkable rubber composition of the present invention is a rubber composition comprising the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) and the SiH group-containing compound (B) Measured by JIS A 5758 (1986)) of 0.1 to 20 MPa.
[58] The fourth crosslinkable rubber composition of the present invention comprises the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A) and the SiH group-containing compound (B) Has an intrinsic viscosity [ ] Of 0.01 to 0.95 dl / g as measured in a decalin solution.
[59] The third crosslinkable rubber composition of the present invention may be the above-mentioned fourth crosslinkable rubber composition.
[60] The third and fourth crosslinkable rubber compositions may be prepared by blending the catalyst (C), the reaction inhibitor (D), the silane coupling agent (E) and the plasticizer (F) It is also good.
[61] The first to fourth crosslinkable rubber compositions of the present invention are very suitably used for electric and electronic parts, transportation equipment, civil engineering and building materials, medical supplies and leisure goods.
[62] Examples of the electric and electronic parts include: sealing materials, potting materials, coating materials, and adhesives used for heavy electrical parts, weak electric parts, circuits and substrates of electric and electronic devices; Repair material for wire covering; Insulating sealing materials for wire joint parts; Roll for 0A appliance; Vibration absorbers; And an encapsulating material of a gel or a condenser.
[63] The sealing material is suitably used for sealing of a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam bath and a circuit breaker.
[64] The potting material is very suitable for potting a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer equipped with a variable resistance, an electric insulating part, a semi-conductive part, a conductive part, a solar battery, and a fly- Is used.
[65] The coating material may include various circuit elements such as a high-voltage thick film resistor and a hybrid IC; HIC; Electrical insulation parts; Semi-conducting parts; Conductive parts; module; Printed circuit; A ceramic substrate; Buffer material of diodes, transistors or bonding wires; Semiconductor device; And for coating optical fibers for optical communication.
[66] The adhesive is very suitably used for the adhesion of cathode ray tube wedges or necks, electrical insulating parts, semiconducting parts and conductive parts.
[67] Uses of the above-mentioned transportation machines include automobiles, ships, airplanes and railway vehicles.
[68] Applications for automobiles include gaskets for automobile engines, electric trim parts and sealants for oil filters; Potting materials for igniter HIC and automotive hybrid IC; Coating materials for automobile bodies, automotive windowpanes and engine control boards; And a gasket of an oil pan; Gaskets for timing belt covers, other automotive gaskets, automotive malls, headlamp lenses, and adhesives for sunroof sealing and mirrors.
[69] Ship uses include wiring connection distribution boxes, electrical system components and wire sealing materials; And adhesives for wires or glass.
[70] Examples of the above civil engineering and architectural uses include butt joints of glass screens of commercial buildings, joints of glass fringes attached to sashes, built-in joints in restrooms, sinks and showcases, joints around bathtubs, Sealant for building materials used in joints of boards; Sealing material for double glass; Civil sealant used to repair roads; Paints and adhesives for metals, glass, stones, slates, concrete and tiles; And an adhesive sheet, a waterproof sheet, and a dustproof sheet.
[71] Examples of applications of the above medical products include a medical rubber stopper, a syringe gasket, and a sealing material for a rubber stopper for blood pressure lowering.
[72] Applications of the above leisure goods include swimming caps for diving masks and ear caps; And gel buffer materials for sports shoes and baseball gloves.
[73] The sealing material, the potting material, the coating material and the adhesive according to the present invention are the first to fourth crosslinkable rubber compositions of the present invention.
[74] BEST MODE FOR CARRYING OUT THE INVENTION
[75] Hereinafter, the crosslinkable rubber composition according to the present invention and its use will be described in detail.
[76] The first crosslinkable rubber composition of the present invention is crosslinkable at room temperature (25 DEG C), has a gelation time at room temperature of 30 days or less, and the crosslinked rubber sheet obtained by crosslinking the composition at room temperature has a tensile elongation (JIS K-6251 ; A measurement temperature of 20 占 폚; a tensile rate of 500 mm / min) of 20% or more; and a crack-free characteristic even after being treated for 96 hours at 40 占 폚 and 50 pphm ozone concentration according to the ozone deterioration test method specified in JIS K- Respectively.
[77] Further, the second crosslinkable rubber composition of the present invention comprises an ethylene / - olefin / nonconjugated polyene random copolymer rubber (A), a SiH group-containing compound (B) having at least two SiH groups in one molecule, Therefore, the catalyst (C), the reaction inhibitor (D), the silane coupling agent (E), and the plasticizer (F) have a gelation time at room temperature of 30 days or less.
[78] The second crosslinkable rubber composition of the present invention, like the first rubber composition of the present invention, is capable of crosslinking at room temperature, having a gelation time at room temperature of 30 days or less, and the crosslinked rubber sheet obtained by crosslinking the composition at room temperature, The elongation is not less than 20%, and even after treatment for 96 hours in an ozone concentration of 40 psi at 50 pphm, there is no crack.
[79] These rubber compositions preferably have a gelation time at room temperature of not more than 30 days, preferably not more than 20 days, more preferably not more than 10 days, more preferably not more than 7 days, further preferably not more than 5 days, particularly preferably not more than 3 Day or less, particularly preferably 2 days or less, and most preferably 1 day or less.
[80] The ethylene / - olefin / non-conjugated polyene random copolymer rubber (A)
[81] The ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) used in the present invention is a random copolymer of ethylene, an -Olefin having 3 to 20 carbon atoms and a nonconjugated polyene.
[82] Examples of the -Olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, -Methyl-1-dodecene and 12-ethyl-1-tetradecene. Of these, -Olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene and 1-octene are particularly preferable.
[83] These -Olefins may be used alone or in combination of two or more.
[84] The nonconjugated polyene used in the present invention is a norbornene compound having a terminal vinyl group represented by the following formula (I) or (II).
[85]
[86] In the formula (I), n is an integer of 0 to 10,
[87] R ¹ is an alkyl group of 1 to 10 carbon atoms or hydrogen atom, and specific examples of the alkyl group having 1 to 10 carbon atoms are methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, sec- butyl, t- butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, nonyl and decyl;
[88] R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
[89] Specific examples of the alkyl group having 1 to 5 carbon atoms for R ² include alkyl groups having 1 to 5 carbon atoms, among the specific examples of R ¹ .
[90]
[91] In the formula (II), R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
[92] Specific examples of the alkyl group for R ³ include the same alkyl groups as the specific examples of the alkyl group for R ¹ above.
[93] Specific examples of the norbornene compound represented by the formula (I) or (II) include
[94] Norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) 5- (1-methyl-3-butenyl) -2-norbornene, 5- (4-pentenyl) Norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl- 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- Pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- , 5- (2-dimethyl-1-hexyl) -2-norbornene, 5- 5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) have. Of these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene is preferable. These norbornene compounds may be used alone or in combination of two or more.
[95] In addition to the above-mentioned norbornene compounds, for example, 5-vinyl-2-norbornene, nonconjugated polyenes may be used in combination as long as the object of the present invention is not impaired.
[96] Specific examples of the nonconjugated polyene include
[97] Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl- Chain nonconjugated dienes such as hexadiene and 7-methyl-1,6-octadiene;
[98] Norbornene, 5-ethylidene-2-norbornene, 5-methylidene-2-norbornene, 5-isopropylidene- Cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene;
[99] Dienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-1-isopropylidene-5-norbornene and 2-propenyl-2,2- .
[100] The ethylene / - olefin / nonconjugated polyene random copolymer (A) having the above components has the following characteristics.
[101] (i) a molar ratio of ethylene and an -olefin having 3 to 20 carbon atoms (ethylene / - olefin)
[102] The ethylene / - olefin / non-conjugated polyene random copolymer rubber (A) is obtained by copolymerizing an ethylene-derived unit (a) and an -Olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as (B) in the range of 40/60 to 95/5, preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and particularly preferably 60/40 to 80/20 In the molar ratio [(a) / (b)].
[103] When the molar ratio is within the above range, it is possible to obtain a rubber composition which is excellent in heat aging resistance, strength characteristics and rubber elasticity, and can provide a crosslinked rubber molded article excellent in cold resistance and workability.
[104] (ii) iodine value
[105] The iodine value of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) is 0.5 to 50 (g / 100 g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 g / 100 g), and particularly preferably 1.5 to 25 (g / 100 g).
[106] When the iodine value is within the above range, a rubber composition capable of providing a rubber composition having a high crosslinking rate at room temperature and capable of providing a crosslinked rubber molded article excellent in compression set resistance and resistance to environmental degradation (thermal aging resistance) Can be obtained. An iodine value of more than 50 is not preferable because it is disadvantageous in terms of cost.
[107] (iii) Intrinsic viscosity
[108] The intrinsic viscosity [ ] Of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) as measured in decalin at 135 ° C is 0.01 to 2 dl / g, preferably 0.02 to 1.8 dl / g, Is preferably 0.05 to 1.5 dl / g, particularly preferably 0.1 to 1.4 dl / g. When the intrinsic viscosity [] is within the above range, a rubber composition excellent in fluidity can be obtained, and a crosslinked rubber molded article excellent in strength characteristics and compression set resistance can be obtained.
[109] The intrinsic viscosity [ ] Is 0.01 to 0.95 dl / g, preferably 0.05 to 0.90 dl / g, more preferably 0.1 to 0.8 dl / g, in terms of moldability, adhesiveness, , And particularly preferably from 0.3 to 0.7 dl / g.
[110] The intrinsic viscosity [ ] Is preferably 0.01 to 0.5 dl / g, more preferably 0.01 dl / g or more and less than 0.3 dl / g, still more preferably 0.3 dl / g or more, from the viewpoints of moldability, adhesiveness, It is preferably in the range of 0.1 to 0.25 dl / g.
[111] (iv) Molecular weight distribution (Mw / Mn)
[112] The molecular weight distribution (Mw / Mn) of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) as measured by GPC is 3 to 100, preferably 3.3 to 75, more preferably 3.5 to 50 to be.
[113] When the molecular weight distribution (Mw / Mn) is within the above range, a rubber composition excellent in workability can be obtained, and a rubber composition capable of providing a crosslinked rubber molded article excellent in strength characteristics can be obtained.
[114] (v) effective net cancellation density (v) [index of crosslinking density]
[115] The effective net cancellation density (ν) measured after press-crosslinking at 170 ° C. for 10 minutes using 0.01 mol of dicumyl peroxide with respect to 100 g of the ethylene / α-olefin / nonconjugated polyene random copolymer rubber (A) Is at least 0.5 x 10 ²⁰ chains / cm ³ , preferably at least 0.8 x 10 ²⁰ chains / cm ³ , more preferably at least 1.0 x 10 ²⁰ chains / cm ³ .
[116] When the effective net cancellation density () is 0.5 x 10 ²⁰ / cm ³ or more, a rubber composition capable of providing a crosslinked rubber molded article excellent in compression set resistance can be obtained.
[117] The ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) is obtained by polymerizing the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A) in the presence of a catalyst containing, as a main component, , A polymerization pressure of 4 to 12 kgf / cm ² , particularly 5 to 8 kgf / cm ² , and a molar ratio (nonconjugated polyene / ethylene) of the feed amount of the non-conjugated polyene to ethylene is 0.01 to 0.2, -olefin and a terminal vinyl group-containing norbornene compound represented by the above formula (I) or (II). The copolymerization is preferably carried out in a hydrocarbon medium.
[118] (H) VO (OR) _n X _{3-n wherein} R is a hydrocarbon group, X is a halogen atom and n is 0 or an integer of 1 to 3, or VX ₄ (X Is a halogen atom).
[119] The soluble vanadium compound (H) is a component soluble in the hydrocarbon medium of the polymerization reaction system. Specific examples thereof include VO (OR) _a X _b or V (OR) _c X _d wherein R is a hydrocarbon group and 0 A 3, 0 b 3, 2 a + b c 4, 0 d 4, 3 c + d 4), and electron donor adducts thereof.
[120] More _{specifically, VOCl 3, VO (OC 2} H 5) Cl 2, VO (OC 2 H 5) 2 Cl, VO (O-iso-C 3 H 7) Cl 2, VO (OnC 4 H 9) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOCl ₃ , VO (OnC ₄ H ₉ ) ₃ and VCl ₃ .2OC ₆ H ₁₂ OH.
[121] (I) R ' _m AlX' _{3-m wherein} R 'is a hydrocarbon group, X' is a halogen atom, and m is 1 to 3.
[122] Specific examples of the organoaluminum compound (I) include
[123] Trialkylaluminum such as triethylaluminum, tributylaluminum and triisopropylaluminum;
[124] Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide;
[125] Alkyl aluminum sesquioalkoxide such as ethyl aluminum sesquistetate and butyl aluminum sesquistetoxide;
[126] _{^{R 1 0.5 Al (OR 1)}} 0.5 such as a partially alkoxylated alkylaluminum having an average composition represented by;
[127] Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide;
[128] Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, and alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, Partially halogenated alkyl aluminum, such as < RTI ID = 0.0 >
[129] Partially hydrogenated alkylaluminums such as dialkylaluminum hydride (e.g., diethylaluminum hydride, dibutylaluminum hydride), and alkylaluminum dihydrides (e.g., ethylaluminum dihydride, propylaluminum dihydride) ;
[130] And partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.
[131] In the present invention, a soluble vanadium compound represented by VOCl ₃ and a compound represented by Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃ Cl ₃ in the compound (I) When an ethylene / - olefin / ethylene / α-olefin having an insoluble content of 1% or less after the Soxylat extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) The non-conjugated polyene random copolymer rubber (A) can be obtained.
[132] As the catalyst used in the copolymerization, for example, a " metallocene catalyst " described in JP-A-9-40586 may be used.
[133] The ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) used in the present invention is graft-modified with a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (for example, an acid anhydride or an ester) It is also good.
[134] Specific examples of such unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic acid .
[135] Specific examples of the acid anhydrides of the unsaturated carboxylic acids include maleic anhydride, itaconic anhydride, citraconic anhydride, anhydrous tetrahydrophthalic acid, and bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic anhydride . Of these, maleic anhydride is preferable.
[136] Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, and dimethyl bicyclo 2,2,1) hept-2-en-5,6-dicarboxylate. Of these, methyl acrylate and ethyl acrylate are preferred.
[137] The graft modifier (graft monomer) such as the above unsaturated carboxylic acid may be used alone or in combination of two or more. In any case, it is used in an amount of not more than 0.1 mol per 100 g of the ethylene / - olefin / non-conjugated polyene copolymer rubber before the graft modification described above.
[138] When the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) having the graft in the above range is used, a rubber composition excellent in flowability (molding processability) can be obtained and a crosslinked rubber molded article A rubber composition which can be provided can be obtained.
[139] The graft-modified ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) is obtained by reacting the above-mentioned unmodified ethylene / - olefin / nonconjugated polyene copolymer rubber and an unsaturated carboxylic acid or a derivative thereof with a radical initiator In the presence of a base.
[140] This grafting reaction can be carried out in a solution state or in a molten state. In the case where the graft reaction is carried out in a molten state, it is most preferable to carry out the graft reaction continuously in the extruder.
[141] Specific examples of the radical initiator used in the grafting reaction include dicumylperoxide, di-t-butylperoxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t- butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl- Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and , '- bis (t-butylperoxy- ;
[142] butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, Peroxyesters such as di-t-butylperoxynaphthalate;
[143] Ketone peroxides such as dicyclohexanone peroxide, and mixtures thereof. Of these, organic peroxides having a half-life of 1 minute at a temperature of 130 to 200 ° C are preferred. Butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumylperoxide, di-t-amylperoxide and t-butylhydroperoxide. Oxide is particularly preferred.
[144] Examples of the polar monomer other than the unsaturated carboxylic acid or its derivative (for example, an acid anhydride, ester) include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, Ester compounds and vinyl chloride.
[145] The SiH group-containing compound (B)
[146] The SiH group-containing compound (B) used in the present invention reacts with the ethylene / alpha -olefin / nonconjugated polyene random copolymer rubber (A) to act as a crosslinking agent. The molecular structure of the SiH group-containing compound (B) is not particularly limited, and dendritic materials conventionally prepared, for example, linear, cyclic, branched, or three-dimensional network structures can be used. However, they must contain at least two, preferably three or more, SiH groups in the molecule, directly bonded to the silicon atoms in the molecule.
[147] As the SiH group-containing compound (B), generally, the following composition formula
[148] R ⁴ _b H _c SiO _{(4-bc) / 2}
[149] Can be used.
[150] In the above formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, exclusive of aliphatic unsaturated bonds. Examples of the monovalent hydrocarbon group include a phenyl group and a halogen-substituted alkyl group (e.g., a trifluoropropyl group) in addition to the alkyl group exemplified as R ¹ above. Of these, methyl, ethyl, propyl, phenyl and trifluoropropyl groups are preferred, with methyl and phenyl groups being particularly preferred.
[151] b is a number satisfying the condition of 0 b <3, preferably 0.6 b 2.2, more preferably 1.5 b c is a number satisfying the condition of 0 < c 3, preferably 0.002 c < 2, more preferably 0.01 c The sum of b and c satisfies 0 <b + c 3, preferably 1.5 <b + c 2.7.
[152] The SiH group-containing compound (B) is preferably an organohydrogenpolysiloxane having 2 to 1000, more preferably 2 to 300, and most preferably 4 to 200, silicon atoms per molecule. Specific examples of these compounds include
[153] Siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane and 1,3,5,7,8-pentamethylpentacosiloxane;
[154] Methylhydrogenpolysiloxanes wherein both ends of the molecular chain are blocked with trimethylsiloxy groups; A dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with trimethylsiloxy groups; Methylhydrogenpolysiloxanes wherein both ends of the molecular chain are blocked with silanol groups; A dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with silanol groups; Dimethylpolysiloxanes wherein both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group; Methylhydrogenpolysiloxanes wherein both ends of the molecular chain are blocked with dimethylhydrogensiloxy groups; A dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group; And
[155] R ⁴ ₂ (H) SiO _1/2 units and SiO _4/2 units, and optionally R ⁴ ₃ SiO _1/2 units, R ⁴ ₂ SiO _2/2 units, R ⁴ (H) SiO _2/2 Units, (H) SiO _3/2 units, or R ⁴ SiO _3/2 units.
[156] Examples of the methylhydrogenpolysiloxane in which both ends of the molecular chain are blocked with trimethylsiloxy groups include compounds represented by the following formulas and compounds obtained by substituting a part or all of the methyl groups with ethyl, propyl, phenyl, or trifluoropropyl groups in the following formula Compounds include:
[157] _{(CH 3) 3 SiO - (} - SiH (CH 3) -O-) d -Si (CH 3) 3
[158] (Wherein d is an integer of 2 or more)
[159] A dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with a trimethylsiloxy group can be obtained by reacting a compound represented by the following formula with a compound represented by the following formula in which a part or all of the methyl group is substituted with ethyl, One compound can be mentioned:
[160] _{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3
[161] (Wherein e is an integer of 1 or more and f is an integer of 2 or more)
[162] Examples of methylhydrogenpolysiloxanes in which both ends of the molecular chain are blocked with a silanol group include compounds represented by the following formulas and compounds obtained by substituting some or all of the methyl groups with ethyl, propyl, phenyl, and trifluoropropyl groups in the following formula Can:
[163] _{HOSi (CH 3) 2 O -} (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH
[164] The dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with a silanol group is obtained by reacting a compound represented by the following formula with a compound represented by the following formula in which some or all of the methyl groups are substituted with ethyl, propyl, phenyl and trifluoropropyl groups Compounds include:
[165] _{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH
[166] (Wherein e is an integer of 1 or more and f is an integer of 2 or more.)
[167] Examples of the dimethylpolysiloxane in which both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group include compounds represented by the following formulas and compounds in which a part or all of the methyl groups are substituted with ethyl, propyl, phenyl and trifluoropropyl groups in the following formula You can:
[168] _{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H
[169] (Wherein e is an integer of 1 or more).
[170] Examples of methylhydrogenpolysiloxanes in which both ends of the molecular chain are blocked with dimethylhydrogensiloxy groups include compounds represented by the following formulas and compounds obtained by substituting a part or all of the methyl groups with ethyl, propyl, phenyl and trifluoropropyl groups Compounds include:
[171] _{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) e -Si (CH 3) 2 H
[172] (Wherein e is an integer of 1 or more).
[173] The dimethylsiloxane / methylhydrogensiloxane copolymer in which both ends of the molecular chain are blocked with a dimethylhydrogensiloxy group can be produced by reacting a compound represented by the following formula with a compound represented by the following formula in which a part or all of the methyl group is substituted with ethyl, A compound substituted with a propyl group;
[174] _{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H
[175] (Wherein e and h are each an integer of 1 or more)
[176] The compound can be prepared by a known method. For example, a compound containing a triosanosilyl group or a diorganohydrogensiloxy group, which may be a terminal group, with octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane (e.g., hexamethyldisiloxane or 1,3 Dihydro-1,1,3,3-tetramethyldisiloxane) in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid at temperatures between -10 ° C and 40 ° C .
[177] The SiH group-containing compound (B) is used in an amount of 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight, and more preferably 0.1 to 100 parts by weight, per 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) More preferably 0.2 to 30 parts by weight, still more preferably 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, and most preferably 0.5 to 5 parts by weight. When the SiH group-containing compound (B) is used in the above range, it is possible to obtain a rubber composition capable of forming a crosslinked rubber molded article having excellent compression set resistance, moderate crosslinking density, and excellent strength and elongation properties . Use of the SiH group-containing compound (B) in a proportion exceeding 100 parts by weight is not preferable because it becomes costly disadvantageous.
[178] The ratio (SiH group / aliphatic unsaturated group) of the SiH groups to the aliphatic unsaturated groups involved in crosslinking of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) is 0.2 to 20, 10, and particularly preferably 0.7 to 5.
[179] The catalyst (C)
[180] The catalyst (C) used as needed in the present invention is an addition reaction catalyst. (A hydrosilylation reaction of an alkene) between the alkenyl group of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A) and the SiH group of the SiH group containing compound (B) There is no limitation. For example, an addition reaction catalyst made of a platinum group element such as a platinum group catalyst, a palladium group catalyst and a rhodium group catalyst (an eighth group metal catalyst such as a Group 8 metal, an eighth group metal complex or a Group 8 metal compound of the periodic table) . Among these, a platinum catalyst is preferred.
[181] The platinum-based catalyst generally uses a known platinum-based catalyst used for addition curing. For example, fine powder metal platinum catalysts described in U.S. Patent No. 2,970,150, chloroplatinic acid catalysts described in U.S. Patent No. 2,823,218, complexes of platinum and hydrocarbons described in U.S. Patent No. 3,159,601 and U.S. Patent No. 159,662, U.S. Patent No. 3,516,946 And the complexes of platinum and vinylsiloxane described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780. More specifically, examples thereof include platinum supported on a support made of platinum (platinum black), chloroplatinic acid, platinum / olefin complex, platinum / alcohol complex, and alumina or silica.
[182] Examples of the palladium-based catalysts include palladium, palladium compounds and palladium chloride chloride. Examples of the rhodium-based catalyst include rhodium, rhodium compounds and rhodium chloride.
[183] Examples of the catalyst (C) other than the above include Lewis acid and cobalt carbonyl.
[184] The catalyst (C) is used in an amount of 0.1 to 100,000 ppm by weight, preferably 0.1 to 10,000 ppm by weight, more preferably 0.1 to 100,000 ppm by weight, based on the ethylene / - olefin / 1 to 5,000 ppm by weight, particularly preferably 5 to 1,000 ppm by weight.
[185] When the catalyst (C) is used in the above range, it is possible to obtain a rubber composition capable of forming a crosslinked rubber molded article having a suitable crosslinking density and excellent strength and elongation properties. Use of the catalyst (C) in an amount exceeding 100,000 ppm by weight is not preferable because it becomes costly disadvantageous.
[186] Further, in the present invention, a crosslinked rubber molded article can be obtained by irradiating an uncrosslinked rubber molded article of the rubber composition containing no catalyst (C) with light, Rays or electron rays.
[187] The reaction inhibitor (D)
[188] In the present invention, the reaction inhibitor (D) is used, if necessary, together with the catalyst (C). Examples of the reaction inhibitor (D) include benzotriazole, ethynyl group-containing alcohols such as ethynylcyclohexanol, acrylonitrile, amide compounds such as N, N-diallylacetamide, N, N, N ', N', N'-tetraallyl-o-phthalic acid diamide, N, N, N ' -Tetralyl-p-phthalic acid diamide), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, and organic peroxides such as hydroperoxides. .
[189] The reaction inhibitor (D) is used in an amount of 0 to 50 parts by weight, usually 0.0001 to 50 parts by weight, preferably 0.001 to 30 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) More preferably from 0.005 to 20 parts by weight, more preferably from 0.01 to 10 parts by weight, particularly preferably from 0.05 to 5 parts by weight.
[190] When the reaction inhibitor (D) is used in a proportion of 50 parts by weight or less, the crosslinking reaction at the initial stage of crosslinking is inhibited and the time required for molding can be ensured, so that a rubber composition excellent in productivity of the crosslinked rubber molded article can be obtained. Use of the reaction inhibitor (D) in a proportion exceeding 50 parts by weight is not preferable because it becomes costly disadvantageous.
[191] Silane coupling agent (E)
[192] In the present invention, a silane coupling agent (E) is used, if necessary, in order to bond the polymer with the filler interface together with the catalyst (C) and to improve the self-adhesiveness of the rubber composition. Examples of the silane coupling agent (E) include a (meth) acrylic functional silane coupling agent, an epoxy functional silane coupling agent, a vinyl functional silane coupling agent, and an amino (imino) functional silane coupling agent.
[193] Specific examples of (meth) acrylic functional silane coupling agents include
[194] Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane , Methacryloylmethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane can be given.
[195] Specific examples of the epoxy functional silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2 - (3,4-epoxycyclohexyl) ethyltriethoxysilane, -Glycidoxypropyltrimethoxysilane, -Glycidoxypropylmethyldiethoxysilane.
[196] Specific examples of the vinyl functional silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (beta -methoxyethoxy) silane.
[197] Specific examples of the amino (imino) functional silane coupling agent include
[198] H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
[199] H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
[200] H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
[201] Amino group and / or imino group-containing alkoxysilane such as (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ;
[202] A reaction product of the amino group and / or imino group-containing alkoxysilane with an epoxy silane compound represented by the following formula;
[203]
[204]
[205] And wherein said amino and / or imino group-containing _{alkoxysilanes, CH 2 = C (CH 3} ) COOCH 2 CH 2 CH 2 Si (OCH 3) 3 and _{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH ₂ CH ₂ OCH ₃ ) ₃ ; a reaction product of a methacryloxy silane compound; And
[206] N-phenyl-gamma -aminopropyltrimethoxysilane.
[207] Among these silane coupling agents,
[208] Vinyl-functional silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (beta -methoxyethoxy) silane;
[209] 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxy-functional silane coupling agents such as ethyltriethoxysilane, -Glycidoxypropyltrimethoxysilane, -Glycidoxypropylmethyldiethoxysilane, and N-phenyl-gamma -aminopropyltrimethoxysilane; And
[210] 3-methacryloxypropyltrimethoxysilane, and (meth) acrylic functional silane coupling agents such as 3-methacryloxypropyltriethoxysilane.
[211] The silane coupling agent (E) is preferably used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the total amount of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) and the SiH group-containing compound (B) , And more preferably 0.1 to 5 parts by weight.
[212] The plasticizer (F)
[213] As the plasticizer (F) used as an optional component in combination with the catalyst (C) in the present invention, a softener commonly used in rubber can be used.
[214] Specific examples of the plasticizer include
[215] Petroleum softeners such as paraffinic process oil, naphthenic process oil, aromatic process oil, ethylene / alpha-olefin co-oligomer, paraffin wax, liquid paraffin, white oil, petrolactum, lubricating oil, petroleum asphalt, and petrolatum;
[216] Coal tar softeners such as coal tar and coal tar pitch;
[217] Oil-based softeners such as castor oil, linseed oil, rapeseed oil and coconut oil;
[218] Tall oil;
[219] Synthetic resin materials such as petroleum resin, atactic polypropylene, and coumarone-indene resin;
[220] Phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-acid derivatives, maleic acid derivatives, fumaric acid derivatives, pyromellitic acid derivatives, , Stearic acid derivatives, phosphoric acid derivatives, sulfonic acid derivatives, glycerin derivatives, glutaric acid derivatives, epoxy derivatives, glycol derivatives, paraffin derivatives and silicone oils.
[221] Of these, ethylene / - olefin co-oligomers, process oils and paraffin derivatives which do not inhibit the silylation reaction are preferred. Particularly preferred are paraffinic process oils and ethylene / alpha-olefin co-oligomers.
[222] The plasticizer (F) is used in an amount of 0 to 1,000 parts by weight, usually 1 to 1,000 parts by weight, preferably 5 to 800 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) More preferably 10 to 700 parts by weight, still more preferably 20 to 500 parts by weight, and particularly preferably 30 to 300 parts by weight.
[223] When the plasticizer (F) is used in the above ratio, fluidity is improved and moldability is improved. When the plasticizer (F) is used in a proportion exceeding 1,000 parts by weight, the strength characteristics are deteriorated, which is not preferable.
[224] Other ingredients
[225] The second to fourth crosslinkable rubber compositions of the present invention can be used in an uncrosslinked state. However, these properties can be most exerted when they are used as a crosslinked product such as a crosslinked rubber molded product and a crosslinked rubber foamed molded product.
[226] The second to fourth crosslinkable rubber compositions of the present invention may contain conventional rubber reinforcing agents, inorganic fillers, antioxidants, processing aids, vulcanization accelerators, organic peroxides, crosslinking aids, foaming agents, An additive such as a colorant, a dispersant, and a flame retardant may be contained in an amount that does not impair the object of the present invention.
[227] The rubber reinforcing agent functions to improve mechanical properties such as tensile strength, tear strength and abrasion resistance of the crosslinked rubber. Examples of the rubber reinforcing agent include carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT and MT; The above carbon black surface-treated with a silane coupling agent or the like; Fine silicic acid; Silica.
[228] Examples of the silica include fumed silica and precipitated silica. These silicas include reactive silanes such as hexamethyldisilazane, chlorosilane, and alkoxysilane; Or may be surface-treated with a low molecular weight siloxane. The specific surface area (BED method) of these silicas is preferably 50 m ² / g or more, and more preferably 100 to 400 m ² / g.
[229] The kind and the compounding amount of these rubber reinforcing agents can be appropriately selected depending on the use thereof. The rubber reinforcing agent is usually used in an amount of at most 300 parts by weight, preferably at most 200 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A).
[230] Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc and clay.
[231] The kind and amount of these inorganic fillers can be appropriately selected depending on the application. The inorganic filler is usually used in an amount of up to 300 parts by weight, preferably up to 200 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A).
[232] Examples of the antioxidant include amine-based, hindered phenol-based, and sulfur-based antioxidants. This antioxidant is used in an amount that does not impair the purpose of the present invention.
[233] Examples of the amine-based antioxidant used in the present invention include diphenylamines and phenylenediamines.
[234] Examples of the diphenylamines include p- (p-toluenesulfonylamide) -diphenylamine, 4,4 '- ( , - dimethylbenzyl) diphenylamine, 4,4'-dioctyldiphenylamine, diphenyl A high temperature reaction product of an amine and an acetone, a low temperature reaction product of diphenylamine and acetone, a low temperature reaction product of diphenylamine and aniline and acetone, a reaction product of diphenylamine and diisobutylene, an octyldiphenylamine, Phenylamine, p, p'-dioctyldiphenylamine, and alkylated diphenylamine.
[235] Examples of phenylenediamines include N, N'-diphenyl-p-phenylenediamine, n-isopropyl-N'-phenyl-p-phenylenediamine, N, -Phenylenediamine, N-phenyl-N'- (3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) Phenylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- And p-phenylenediamines such as phenylenediamine.
[236] Among these, 4,4 '- ( , - dimethylbenzyl) diphenylamine and N, N'-di-2-naphthyl-p-phenylenediamine are particularly preferable.
[237] These compounds may be used alone or in combination of two or more.
[238] Examples of the hindered phenolic antioxidant include
[239] (1) 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
[240] (2) 4,4'-butylidenebis- (3-methyl-6-t-butylphenol)
[241] (3) 2,2-thiobis (4-methyl-6-t-butylphenol)
[242] (4) 7-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate,
[243] (5) tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane,
[244] (6) pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
[245] (7) triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate]
[246] (8) 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
[247] (9) Synthesis of 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl anilino) -1,3,5-
[248] (10) tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate,
[249] (11) 2,2-thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
[250] (12) N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy) -hydrocinnamide,
[251] (13) 2,4-bis [(octylthio) methyl] -o-cresol,
[252] (14) 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate-diethyl ester,
[253] (15) Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] Methane,
[254] (16) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate,
[255] (17) Synthesis of 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] - tetraoxaspiro [5,5] undecane
[256] .
[257] Among them, phenol compounds of (5) and (17) are particularly preferable.
[258] Examples of the sulfur-based antioxidant include sulfur-based antioxidants commonly used in rubber.
[259] Examples of the sulfur-based antioxidant include
[260] Mercaptobenzimidazole, the zinc salt of 2-mercaptobenzoimidazole, the zinc salt of 2-mercaptomethylbenzoimidazole, the zinc salt of 2-mercaptomethylbenzimidazole, the zinc of 2-mercaptobenzimidazole, Imidazole-based antioxidants such as salts; And
[261] Diallyl thiodipropionate, distearyl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropio Aliphatic thioether-based antioxidants such as N-methylpyrrolidone. Among them, in particular, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, 2-mercaptomethylbenzoimidazole, zinc salt of 2-mercaptomethylbenzoimidazole, pentaerythritol-tetrakis - (beta -lauryl-thiopropionate).
[262] As the above-mentioned processing aid, a compound used for ordinary rubber processing can be used.
[263] Examples of the processing aid include
[264] Higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid;
[265] Salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate;
[266] And esters of higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid.
[267] The processing aid is usually used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A). The optimum amount of this is appropriately determined according to the required characteristic value.
[268] In the present invention, both the addition crosslinking and the radical crosslinking may be carried out by using an organic peroxide in addition to the catalyst (C). The organic peroxide is used in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A). As the organic peroxide, conventionally known organic peroxides commonly used in the crosslinking of rubber can be used.
[269] When an organic peroxide is used, it is preferable to use a crosslinking aid in combination.
[270] Examples of crosslinking aids include
[271] Sulfur; quinonedioxime compounds such as p-quinonedioxime; Methacrylate compounds such as polyethylene glycol dimethacrylate; Allyl compounds such as diallyl phthalate and triallyl cyanurate; Maleimide compounds; And divinylbenzene.
[272] The crosslinking aid is used in an amount of 0.5 to 2 moles, preferably approximately equimolar, per 1 mole of the organic peroxide to be used.
[273] As the foaming agent,
[274] Inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and ammonium nitrite;
[275] Nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide and N, N'-dinitrosopentamethylenetetramine;
[276] Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexyl nitrile, azodiaminobenzene, and barium azodicarboxylate;
[277] Sulfonylureas such as benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), and diphenylsulfone-3,3'-disulfonylhydrazide. Drazide compounds;
[278] Azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide and p-toluenesulfonyl azide; And
[279] Carbon dioxide, nitrogen, oxygen, and chlorofluorocarbons.
[280] These blowing agents are used in a proportion of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A). When the foaming agent is used in the above ratio, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced. The optimum amount of this is desirably determined appropriately according to the required characteristic value.
[281] If necessary, a foaming auxiliary may be used in combination with the foaming agent. The foaming aid acts to lower the decomposition temperature of the foaming agent, accelerate the decomposition, and uniform the bubbles.
[282] Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid; Element or a derivative thereof. These foaming assistants are used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A). It is preferable that the optimum amount thereof is appropriately determined according to the required characteristic value.
[283] Further, other known rubbers may be blended into the second to fourth crosslinkable rubber compositions according to the present invention so long as the object of the present invention is not impaired.
[284] Examples of the rubber include isoprene rubber such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber CR), and the like.
[285] Further, conventionally known ethylene / - olefin-based copolymer rubbers may be used. For example, an ethylene / - olefin / polyene copolymer (for example, EPDM) other than the ethylene / propylene random copolymer (EPR) and the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) Can be used.
[286] Rubber compositions and uses thereof
[287] The first to fourth crosslinkable rubber compositions of the present invention are used for electric and electronic parts, transportation equipment, civil engineering and building products, medical supplies and leisure products.
[288] The electric and electronic parts may be used as sealing materials, potting materials, coating materials or adhesive materials used for circuits or substrates of heavy electric parts, weak electric parts, electric and electronic devices; Repair material for wire covering; Insulating sealing materials for wire joint parts; Roll for 0A appliance; Vibration absorbers; And an encapsulating material of a gel or a condenser.
[289] The sealing material is suitably used for a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam damper and an electric leakage breaker.
[290] The potting material is suitably used for potting a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer equipped with a variable resistance unit, an electric insulating part, a semi-conductive part, a conductive part, a solar battery and a flyback transformer for a TV.
[291] The coating material may be various circuit elements such as high-voltage thick-film resistors and hybrid ICs; HIC; Electrical insulation parts; Semi-conducting parts; Conductive parts; module; Printed circuit; Ceramic substrates; buffer materials for diodes, transistors and bonding wires; Semiconductor device; And for coating optical fibers for optical communication.
[292] The adhesive is suitably used for bonding a cathode ray tube wedge or neck, an electrically insulating part, a semiconducting part and a conductive part.
[293] The transporter may be an automobile, a ship, an aircraft, or a railway vehicle.
[294] Automotive applications include gaskets for automotive engines, electrical components and sealants for oil filters; Potting material for igniter HIC and hybrid IC for automobiles; Coating materials for automobile body, automobile window and engine control board; And gaskets for oil pan or timing belt covers, automobile malls, head lamp lenses, sunroof sealing and mirrors.
[295] Ship applications include wiring connection distribution boxes, electrical system components, and seaming materials for wires; Adhesives for wire or glass.
[296] The above civil engineering and architectural uses include glass joints of commercial buildings, joints of glass fringes fixed to sashes, built-in joints in restrooms, wash basins or showcases, joints around bathtubs, exterior wall expansion joints and siding Sealant for building materials used in joints for boards; Sealing material for double glass; Civil sealant used to repair roads; Paints and adhesives for metals, glass, stones, slates, concrete and tiles; An adhesive sheet; A waterproof sheet and a dustproof sheet.
[297] Uses of the above medical supplies include a medical rubber stopper, a syringe gasket, and a rubber stopper for dropping blood pressure.
[298] Examples of applications of the above-mentioned leisure products include swiming members such as a swimming cap, a diving mask and an ear plug; Sports shoes and baseball gloves.
[299] The first to fourth crosslinkable rubber compositions of the present invention can be suitably used as sealing materials, potting materials, coating materials and adhesives, which are added to electric and electronic parts, transportation equipment, civil engineering construction materials, medical supplies and leisure products respectively.
[300] Rubber composition and production of the crosslinked rubber molded article
[301] As described above, the second to fourth crosslinkable rubber compositions of the present invention can be used in an uncrosslinked state. However, these properties can be most exerted when used as a crosslinked product (vulcanized product) such as a crosslinked rubber molded article or a crosslinked rubber foamed molded article.
[302] In order to produce a crosslinked product from the second to fourth crosslinkable rubber compositions of the present invention, the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A), SiH Depending on the use of the group-containing compound (B) and, if necessary, the catalyst (C), the reaction inhibitor (D), the silane coupling agent (E), the plasticizer (F), and the intended crosslinked product, conventionally known rubber reinforcing agents, An additive such as a filler, an antioxidant, a processing aid, a vulcanization accelerator, an organic peroxide, a crosslinking auxiliary, a foaming agent, a foaming auxiliary, a colorant, a dispersant and a flame retardant; Then, the compounded rubber is molded into an intended shape (filling the compounded rubber into the gap, inserting the compounded rubber between the articles, coating the compounded rubber on the article, or porting the article); (Vulcanizing) the resultant product by leaving it at room temperature. It may also be warmed to accelerate the crosslinking reaction.
[303] Specifically, the second to fourth crosslinkable rubber compositions of the present invention can be obtained by melt kneading an ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) with a kneader such as a planetary mixer and a kneader, , The SiH group-containing compound (B) and, if necessary, the catalyst (C), the reaction inhibitor (D), the silane coupling agent (E), the plasticizer (F) , An inorganic filler, an anti-aging agent, a processing aid, a vulcanization accelerator, an organic peroxide, a crosslinking assistant, a foaming agent, a foaming aid, a colorant, a dispersant and a flame retardant.
[304] In the present invention, the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) can be kneaded at a high temperature with the rubber reinforcing agent and the inorganic filler. On the other hand, if the SiH group-containing compound (B) and the catalyst (C) are simultaneously kneaded at a high temperature, crosslinking (scorch) may occur. Therefore, when the SiH group-containing compound (B) and the catalyst (C) are mixed at the same time, it is preferable to knead at 80 캜 or lower. When the SiH group-containing compound (B) and the catalyst (C) are added one by one, they can be kneaded at a temperature exceeding 80 캜. It is also preferable in some cases to cool the heat generated by the kneading with the cooling water.
[305] The thus-prepared second to fourth crosslinkable rubber compositions of the present invention can be obtained by filling them in a gap, inserting them between an object and an object, coating them on an object, or potting an object, A roll, a press, an injection molding machine, a transfer molding machine, or the like. Thereafter, the molded article is allowed to stand at room temperature to carry out crosslinking, whereby a desired crosslinked product (crosslinked rubber molded article) can be obtained. It may also be warmed to accelerate the crosslinking reaction.
[306] Effects of the Invention
[307] The first crosslinkable rubber composition of the present invention has a high crosslinking speed at room temperature and is excellent in adhesiveness, in particular, adhesion with an inorganic substance such as metal, and can be produced with productivity that satisfies a crosslinked rubber molded article (including a foamed article) . The crosslinked rubber molded article has a high tensile elongation and is excellent in weather resistance, ozone resistance, heat aging resistance, compression set resistance and gas permeability.
[308] The second to fourth crosslinkable rubber compositions of the present invention have a high crosslinking speed at room temperature, are excellent in productivity, exhibit excellent adhesiveness, particularly, adhesion with an inorganic substance such as a metal, and are excellent in weather resistance, ozone resistance, It is possible to manufacture a crosslinked rubber molded article (including a foamed article) having excellent compression set resistance and gas permeability at low cost.
[309] The first to fourth crosslinkable rubber compositions according to the present invention have the above-mentioned effects, and thus are suitably used for electric and electronic parts, transportation equipment, civil engineering and building materials, medical supplies or leisure products. These specific uses are as described above. These rubber compositions are excellent in moldability and adhesiveness in addition to the above-mentioned properties, and are therefore very suitable for sealing materials.
[1] The present invention relates to rubber compositions which are crosslinkable at room temperature and their use. More specifically, the present invention relates to a crosslinked rubber molded article which can produce a crosslinked rubber molded article with a high crosslinking speed at room temperature, can efficiently produce a crosslinked rubber molded article, and can produce a crosslinked rubber molded article excellent in weatherability, ozone resistance, heat aging resistance and compression set resistance To crosslinkable rubber compositions and their use. Further, the present invention relates to a crosslinkable rubber composition which is excellent in moldability and adhesiveness in addition to the above properties, and which is very suitable as a sealing material, and the use thereof.
[310] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.
[311] The composition, the iodine value, the intrinsic viscosity [ ], The molecular weight distribution (Mw / Mn), the net net cancellation density ( ) And the adhesive strength of the copolymer rubber used in this Example and Comparative Example were measured by the following methods.
[312] (1) Composition of copolymer rubber
[313] The composition of the copolymer rubber was measured by ¹³ C-NMR.
[314] (2) Iodine Value of Copolymer Rubber
[315] The iodine value of the copolymer rubber was determined by a titrimetric method.
[316] (3) Intrinsic viscosity [ ]
[317] The intrinsic viscosity [ ] Of the copolymer rubber was measured in decalin at 135 占 폚.
[318] (4) Molecular weight distribution (Mw / Mn)
[319] The molecular weight distribution of the copolymer rubber is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), as determined by GPC. In GPC, GMH-HT and GMH-HTL (manufactured by Tosoh) were used as columns, and o-dichlorobenzene was used as a solvent.
[320] (5) Effective net cancellation density (v)
[321] The polymer rubber was immersed in toluene at 37 占 폚 for 72 hours according to JIS K6258 (1993), and the net net cancellation density was calculated according to the equation of Flory-Rehner.
[322] (chain / cm ³ ) = _R + ln (1- _R ) + v _R ² / -V _O ( _R ^1/3 - _R / 2)
[323] ν _R : Volume fraction of pure rubber to the volume of the swollen pure rubber in the swollen crosslinked rubber (the volume of the pure rubber + the volume of the absorbed solvent)
[324] μ: Interaction constant between rubber and solvent = 0.49
[325] Vo: molecular volume of solvent
[326] ν (number / cm ³ ): effective net cancellation density. Number of effective net cancellation in 1 cm ³ of neat rubber.
[327] Preparation of sample: 0.01 g of dicumyl peroxide was added to 100 g of the copolymer rubber, and the mixture was kneaded at a kneading temperature of 50 占 폚 using an 8-inch roll open roll according to the method described in the Japanese Rubber Association Standard (SRIS) The kneaded product thus obtained was press-crosslinked at 170 DEG C for 10 minutes to prepare a sample.
[328] (6) Adhesive strength
[329] After the composition shown below was prepared, the adhesive strength of the composition was measured based on the tensile adhesion test of JIS A 5758 (1986). The curing conditions were a reaction curing two-component type. Aluminum was selected as the adherend.
[330] &Lt; Preparation of composition >
[331] 100 parts by weight of various polymers and 20 parts by weight of the carbon black (trade name: Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.) were kneaded at 80 DEG C for 20 minutes by using a 2 liter capacity planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) . The filling rate was 50%. After the obtained mixture was cooled to room temperature, 3 parts by weight of tris (dimethylhydroxyloxy) phenylsilane [C ₆ H ₅ -Si- (O-SiH- (CH ₃ ) ₂ ) was kneaded at room temperature for 10 minutes, 0.1 part by weight of hexachloroplatinic acid (2% isopropanol solution) was kneaded at room temperature for 5 minutes to obtain a composition.
[332] Production Example 1
[333] [Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1)
[334] Propylene and 5-vinyl-2-norbornene were successively copolymerized using a 100 liter stainless steel polymerization machine (agitation rotation speed = 250 rpm) equipped with a stirring blade. 60 liters of hexane, 3.0 kg of ethylene, 9.0 kg of propylene, 550 g of 5-vinyl-2-norbornene, 50 liters of hydrogen, 95 mmol of VOCl ₃ as a catalyst, 443 millimoles of (Et) ₂ Cl, and 127 millimoles of Al (Et) _1.5 Cl _1.5 were continuously supplied.
[335] Copolymerization was carried out under the above conditions to obtain an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) in a homogeneous solution state.
[336] Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the bottom of the polymerization reactor to terminate the polymerization reaction. The polymer was separated from the solvent by steam stripping treatment, and vacuum dried at 55 캜 for 48 hours.
[337] The properties of the obtained ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) thus obtained are shown in Table 1.
[338] Production Examples 2 to 3
[339] The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-2) having different properties was obtained in the same manner as in Production Example 1 except that the polymerization conditions were changed as shown in Table 1. (A-3). The properties of the obtained copolymer rubber (A-2) and (A-3) are shown in Table 1.
[340] <Table 1>
[341] Copolymer rubberA-1A-2A-3 catalystVOCl ₃ -Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 VOCl ₃ -Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 VOCl ₃ -Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5Al / V666 Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 7/27/27/2 Polymerization temperature (캜)404040 Polymerization pressure (kgf / cm ² )7.17.17.2 Catalyst feed rate (mmol / hr)954590 DienVNBVNBVNB Diene feed (g / hr)550330550 alpha -olefinPropylenePropylenePropylene Feed amount of ethylene / - olefin (kg / hr)3.0 / 9.03.0 / 9.52.8 / 11.5 H ₂ (NL / hr)705040 Yield (kg / hr)3.54.54.1 Ethylene content (mol%)686863 [ ] (dl / g)0.20.71.1 IV (g / 100g)151015 Mw / Mn152840 Effective net cancellation density ν (× 10 ¹⁹ / cm ³ )0.81.22.5
[342] Note 1) VNB: 5-vinyl-2-norbornene
[343] 2) Et: ethoxy group
[344] 3) IV: iodine value
[345] Example 1
[346] First, 100 parts by weight of an ethylene / - olefin / nonconjugated polyene random copolymer rubber (A-1) shown in Table 1, 100 parts by weight of C ₆ H ₅ Si (-OSiMe ₂ H) ₃ (B) [Shinetsu Chemical Industries , And 0.3 parts by weight of a 2% chloroplatinic acid isopropyl alcohol solution (C) were kneaded at room temperature using a laboratory mill and a twin mill to prepare a compounded rubber.
[347] The resulting compounded rubber was subjected to a gelation test, and the gelation time at room temperature was measured. The results are shown in Table 3.
[348] Further, the obtained compounded rubber was cast in a metal frame having a depth of 2 mm, and then left at room temperature for 3 days to obtain a crosslinked sheet having a thickness of 2 mm.
[349] The obtained crosslinked sheet was subjected to a tensile test and an ozone deterioration test in the following manner.
[350] (1) Gelation test
[351] The change in frequency was measured using a scanning VNC (SVNC) (manufactured by Rapra Technology Co.). The frequency was increased with this measurement, and the time when the frequency was stabilized was set to 100%, and the time when the frequency was changed by 95% was set as the gelation time (crosslinking time). The measurement temperature was room temperature, and the measurement was carried out in accordance with the following documents.
[352] (i) Operation Manual (Software Version 2.2) of RAPRA Scanning Vibration Erosion Curing Tester (Scanning VNC)
[353] (ii) Understanding of curing of RAPRA Scanning Vibration Erosion Curing Tester (Scanning VNC) (RTL / 2844)
[354] (2) Tensile test
[355] A tensile strength T _B and a tensile elongation E _B at the time of breaking of the crosslinked sheet were measured according to JIS K-6251 under the conditions of a measurement temperature of 23 ° C and a tensile rate of 500 mm / min.
[356] (3) Ozone Degradation Test
[357] The ozone deterioration test was carried out in accordance with JIS K-5259. This test condition is 96 hours at 40 캜 and 50 pphm ozone concentration.
[358] These results are shown in Table 2.
[359] Further, the adhesive strength of the composition of the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A-1) to aluminum was measured by the above method. As a result, the adhesive strength was 1.5 MPa
[360] Example 2
[361] Except that the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) shown in Table 1 was used in place of the ethylene / propylene / The procedure of Example 1 was repeated except that the rubber (A-2) was used and 120 parts by weight of a plasticizer (F) (trade name: Idemitsu Diana Process Oil PW-32 manufactured by Idemitsu Kosan Co., Ltd.) was added. The results are shown in Table 2.
[362] Further, the adhesive strength of the composition of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A-2) to aluminum was measured according to the above method. As a result, the adhesive strength was 2.5 MPa
[363] Example 3
[364] Except that the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) shown in Table 1 was used in place of the ethylene / propylene / The procedure of Example 1 was repeated except that the rubber (A-3) was used and 300 parts by weight of a plasticizer (F) [Idemitsu Diana Process Oil PW-32 (manufactured by Idemitsu Kosan Co., Ltd.) was added. The results are shown in Table 2.
[365] Further, the adhesive strength of the composition of the ethylene / - olefin / non-conjugated polyene random copolymer rubber (A-3) to aluminum was measured by the above method. As a result, the adhesive strength was less than 0.1 MPa.
[366] Example 4
[367] Except that 0.01 part by weight of ethynylcyclohexanol (D) and 5 parts by weight of 3-glycidoxypropyltrimethoxysilane (E) were added. The results are shown in Table 2.
[368] Example 5
[369] The amount of the plasticizer (F) to be added was changed from 300 parts by weight to 400 parts by weight, and 0.01 part by weight of ethynylcyclohexanol (D), 5 parts by weight of 3-glycidoxypropyltrimethoxysilane (E) Except that 50 parts by weight of silica (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) was added. The results are shown in Table 2.
[370] Comparative Example 1
[371] Except that an ethylene / propylene / 5-ethylidene-2-norbornene random copolymer rubber (A-1) was used in place of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber -4) [trade name: Mitsui EPT X-4010, manufactured by Mitsui Chimical Co., Ltd.] was used. The results are shown in Table 2.
[372] Comparative Example 2
[373] Except that an ethylene / propylene / dicyclopentadiene copolymer rubber (A-5) (trade name: Mitsui) was used in place of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A- EPT X-3012P, manufactured by Mitsui Chimical Co., Ltd.] was used. The results are shown in Table 2.
[374] Comparative Example 3
[375] Except that the polyisoprene copolymer rubber (A-6) prepared in the following manner was used in place of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A- Was carried out in the same manner as in Example 1. The results are shown in Table 2.
[376] Preparation of polyisoprene copolymer rubber (A-6)
[377] To a reaction vessel charged with 300 g of hydrogenated polyisoprene having a hydrosilyl group at the end of a terminal [Idemitsu Petrochemicals Co., Ltd., trademark: Epol], 50 ml of toluene was added, dehydrated by azeotropic deaeration, 48 g of t- BuOK was added to 200 ml of THF Dissolved solution was injected.
[378] After reacting the hydrogenated polyisoprene with t-BuOK at 50 占 폚 for 1 hour, 47 ml of allyl chloride was added dropwise to the reaction solution over about 30 minutes. After completion of the dropwise addition, 30 g of aluminum silicate was added to the reaction solution to absorb the generated salt, and the mixture was stirred at room temperature for 30 minutes.
[379] Then, this mixture was filtered and purified to obtain about 250 g of hydrogenated polyisoprene having an ally group at the terminal. The iodine value determined by the iodometric titration method thereof was 0.1 mol / 100 g.
[380] Comparative Example 4
[381] Instead of 4.3 parts by weight of C ₆ H ₅ Si (-OSiMe ₂ H) ₃ (B) [manufactured by Shinetsu Chemical Industries, Ltd.] and 0.3 part by weight of 2% chloroplatinic acid isopropyl alcohol solution (C) Was used in an amount of 2.7 parts by weight. The results are shown in Table 2.
[382] Comparative Example 5
[383] , 4.3 parts by weight of C ₆ H ₅ Si (-OSiMe ₂ H) ₃ (B) [manufactured by Shinetsu Chemical Industries, Ltd.] and 0.3 part by weight of 2% chloroplatinic acid isopropyl alcohol solution (C) 0.5 part by weight of 2-mercaptobenzothiazole [Sanshin Chemical Industries, Ltd., trade name: Sanceler M], 1.0 part by weight of tetramethylthiuram disulfide [Sanshin Chemical Industries, Inc., trade name: Sanceler TT], 5 parts by weight of zincation, Was used in place of 1 part by weight of the resin composition. The results are shown in Table 2.
[384] <Table 2>
[385] Example One2345 Composition (parts by weight) The copolymer rubber (A-1)100 The copolymer rubber (A-2) 100 100Copolymer rubber (A-3) 100 100 Copolymer rubber (A-4)Copolymer rubber (A-5)Copolymer rubber (A-6)C ₆ H ₅ Si (-OSiMe ₂ H) ₃ (B)4.34.34.34.34.3 IPA solution of 2% chloroplatinic acid (C)0.30.30.30.30.3 Ethynylcyclohexanol (D) 0.010.01 3-GPTMS (E) 55 PW-32 (F) 120300120400 Dicyclohexyl oxidesulfurSanceler-MSanceler-TTZincificationStearic acidAerosil 20050 The crosslinking speed (t _c (90) [min]1521293952 Ozone resistanceNo crackNo crackNo crackNo crackNo crack T _B [MPa]0.30.40.40.40.8 E _B [%]60250380300240
[386] <Table 2> (Continued)
[387] Comparative Example One2345 Composition (parts by weight) The copolymer rubber (A-1)The copolymer rubber (A-2) 100100 Copolymer rubber (A-3)Copolymer rubber (A-4)100 Copolymer rubber (A-5) 100 Copolymer rubber (A-6) 100 C ₆ H ₅ Si (-OSiMe ₂ H) ₃ (B)4.34.34.3 IPA solution of 2% chloroplatinic acid (C)0.30.30.3 Ethynylcyclohexanol (D)3-GPTMS (E)PW-32 (F) 120120 Dicyclohexyl oxide 3.5sulfur1.5 Sanceler-M0.5 Sanceler-TTOne Zincification5 Stearic acidOne Aerosil 200The crosslinking speed (t _c (90) [min]1000 <1000 <1051000 <1000 < Ozone resistanceLack of bridgeLack of bridgeA-2Lack of bridgeLack of bridge T _B [MPa]0.40.1> 10.1> E _B [%]1201200900
[388] Note: In the component (B), Me: methyl group
[389] IPA in component (C): isopropyl alcohol
[390] 3-GPTMS in component (E): 3-glycidoxypropyltrimethoxysilane
[391] <Table 3>
[392] Gelation time (hrs) at room temperature Example 115 Example 221 Example 329 Example 439 Example 552 Comparative Example 11000 < Comparative Example 21000 < Comparative Example 3105 Comparative Example 41000 < Comparative Example 51000 <

权利要求:
Claims (25)
[1" claim-type="Currently amended] A rubber composition capable of crosslinking at room temperature, wherein a gelation time at room temperature is 30 days or less,
The crosslinked rubber sheet obtained by crosslinking the composition at room temperature had a tensile elongation (JIS K-6Z51; measurement temperature: 20 캜, tensile speed: 500 mm / min) of 20% or more and an ozone deterioration test method specified in JIS K-5259 , A crack-free property on the crosslinked rubber sheet after being treated for 96 hours in an ozone concentration of 50 pphm at 40 占 폚.
[2" claim-type="Currently amended] (A) an ethylene / - olefin / non-conjugated polyene random copolymer having a constitutional unit derived from at least one terminal vinyl group-containing norbornene compound represented by the following formula (I) or A combination rubber (A)

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

(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms),
(B) a SiH group-containing compound having at least two SiH groups in one molecule
Respectively,
Wherein the gelation time at room temperature is 30 days or less.
[3" claim-type="Currently amended] 3. The method according to claim 1 or 2,
Wherein the rubber composition has an adhesion strength to aluminum (measured according to JIS A 5758 (1986)) of 0.1 to 20 MPa.
[4" claim-type="Currently amended] 4. The method according to any one of claims 1 to 3,
Wherein the ethylene / - olefin / nonconjugated polyene random copolymer rubber (A) has an intrinsic viscosity [ ] Of 0.01 to 0.95 dl / g as measured in a decalin solution at 135 占 폚.
[5" claim-type="Currently amended] (A) an ethylene / - olefin / non-conjugated polyene random copolymer having a constitutional unit derived from at least one terminal vinyl group-containing norbornene compound represented by the following formula (I) or A combination rubber (A)

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

(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms),
(B) a SiH group-containing compound having at least two SiH groups in one molecule
As a rubber composition
A crosslinkable rubber composition having an adhesion strength (measured according to JIS A 5758 (1986)) of 0.1 to 20 MPa with aluminum of the rubber composition;
[6" claim-type="Currently amended] (A) an ethylene / - olefin / non-conjugated polyene random copolymer having a constitutional unit derived from at least one terminal vinyl group-containing norbornene compound represented by the following formula (I) or A combination rubber (A)

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

(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms),
(B) a SiH group-containing compound having at least two SiH groups in one molecule
As a rubber composition,
Wherein the copolymer rubber (A) has an intrinsic viscosity [ ] Of 0.01 to 0.95 dl / g as measured in a decalin solution at 135 占 폚.
[7" claim-type="Currently amended] (A) an ethylene / - olefin / non-conjugated polyene random copolymer having a constitutional unit derived from at least one terminal vinyl group-containing norbornene compound represented by the following formula (I) or A combination rubber (A)

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

(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms),
(B) a SiH group-containing compound having at least two SiH groups in one molecule
As a rubber composition,
(Measured by JIS A 5758 (1986)) of the rubber composition with aluminum is from 0.1 to 20 MPa and the intrinsic viscosity of the copolymer rubber (A) measured in a decalin solution at 135 캜 ] is 0.01 to 0.95 dl / g.
[8" claim-type="Currently amended] 8. The method according to any one of claims 2 to 7,
The rubber composition
(A) an ethylene / - olefin / nonconjugated polyene random copolymer rubber,
(B) a SiH group-containing compound having at least two SiH groups in one molecule,
(C) a catalyst,
(D) an inhibitor or
(E) Silane coupling agent
By weight.
[9" claim-type="Currently amended] 8. The method according to any one of claims 2 to 7,
Wherein the rubber composition has the characteristics described in claim 1.
[10" claim-type="Currently amended] 8. The method according to any one of claims 1 to 7,
Wherein the rubber composition is used for electrical and electronic parts, transportation, civil engineering and building materials, medical or leisure applications.
[11" claim-type="Currently amended] 11. The method of claim 10,
The use of the above electrical and electronic parts is not limited to the use of heavy electrical parts, weak electrical parts, sealing materials for circuits or substrates of electrical and electronic equipment, potting materials, coating materials or adhesives; Repair material for wire covering; Insulating sealing materials for wire joint parts; Roll for 0A appliance; Vibration absorbers; And an encapsulating material for a gel or a condenser.
[12" claim-type="Currently amended] 12. The method of claim 11,
Wherein the sealing material is used for a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam damper and an earth leakage breaker.
[13" claim-type="Currently amended] 12. The method of claim 11,
Wherein the potting material is used for potting a transformer high voltage circuit, a printed circuit board, a high voltage transformer equipped with a variable resistance portion, an electrically insulating part, a semiconducting part, a conductive part, a solar battery, and a flyback transformer for a TV.
[14" claim-type="Currently amended] 12. The method of claim 11,
Wherein the coating material is a high-voltage thick-film resistor and a circuit element of a hybrid IC; HIC; Electrical insulation parts; Semi-conducting parts; Conductive parts; module; Printed circuit; A ceramic substrate; Buffer material of diodes, transistors or bonding wires; Semiconductor device; And an optical fiber for optical communication.
[15" claim-type="Currently amended] 12. The method of claim 11,
Wherein the adhesive is used for bonding a cathode tube wedge or neck, an electrically insulating part, a semiconductive part, and a conductive part.
[16" claim-type="Currently amended] 11. The method of claim 10,
Wherein the use of said transporter is for use in an automobile, a vessel, an aircraft and a railway vehicle.
[17" claim-type="Currently amended] 17. The method of claim 16,
Wherein the use of the automobile is a sealing material for a gasket, an electric component or an oil filter of an automobile engine; Potting materials for igniter HIC and automotive hybrid IC; Coating materials for automobile bodies, automotive windowpanes and engine control boards; And a gasket of an oil pan, a gasket of a timing belt cover, an automobile mall, a head lamp lens, a sunroof sealing or a mirror.
[18" claim-type="Currently amended] 17. The method of claim 16,
The use of the ship is a wiring connection distribution box, an electrical system part and a sealing material for electric wires; And an adhesive for wire or glass.
[19" claim-type="Currently amended] 11. The method of claim 10,
The above civil engineering and architectural uses are customized joints of glass screen of commercial buildings, joints of glass fringe fixed to sashes, built-in joints in restrooms, sleeping pads or showcases, joints around bathtubs, exterior wall expansion joints for assembly houses, siding boards Sealant for building materials used in joints; Sealing material for double glass; Civil sealant used to repair roads; Paints and adhesives for metals, glass, stones, slates, concrete and tiles; And a crosslinkable rubber composition which is used as a pressure-sensitive adhesive sheet, a waterproof sheet and a dustproof sheet.
[20" claim-type="Currently amended] 11. The method of claim 10,
Wherein the use of said medical treatment is a sealing material for a medical rubber stopper, a syringe gasket and a blood stopping rubber stopper.
[21" claim-type="Currently amended] 11. The method of claim 10,
Wherein the use of the leisure is a swimming cap for a swimming cap, a diving mask or an ear plug; And a gel buffer material for a sports shoe or baseball glove.
[22" claim-type="Currently amended] A sealing material comprising a crosslinkable rubber composition according to any one of claims 1 to 9.
[23" claim-type="Currently amended] A potting material comprising the crosslinkable rubber composition according to any one of claims 1 to 9.
[24" claim-type="Currently amended] A coating material comprising a crosslinkable rubber composition comprising the crosslinkable rubber composition according to any one of claims 1 to 9.
[25" claim-type="Currently amended] An adhesive comprising the crosslinkable rubber composition according to any one of claims 1 to 9.

类似技术:

---

公开号 | 公开日 | 专利标题

---

JP5946515B2|2016-07-06|4-methyl-1-pentene / α-olefin copolymer composition

---

JP5755309B2|2015-07-29|Release film and sheet

---

US5164461A|1992-11-17|Addition-curable silicone adhesive compositions

---

CA2623543C|2012-05-22|Use of a cautchouc compound as material in the field of fuel cells

---

JP2012180522A|2012-09-20|Curable resin composition for semiconductor package, and semiconductor

---

DE60111147T2|2006-05-04|High and low molecular weight EPDM rubber

---

US8569429B2|2013-10-29|Curable silicone resin composition with high reliability and optical semiconductor device using same

---

CN1240761C|2006-02-08|Crosslinkable rubber composition and use thereof

---

EP1505121B1|2008-01-09|Hardenable composition, hardening product, process for producing the same and light emitting diode sealed with the hardening product

---

US9698320B2|2017-07-04|Modified product of polyhedral structure polysiloxane, polyhedral structure polysiloxane composition, cured product, and optical semiconductor device

---

EP1938407B1|2010-11-17|Use of a elastomer blend as a material in the insertion area of the fuel cells

---

JP5666775B2|2015-02-12|Polysiloxane composition, molded article obtained from the same, and optical device member

---

CN101883819B|2013-03-20|Rubber composition, crosslinked product and foam thereof, molded product therefrom, and use thereof

---

EP1464670B9|2007-03-21|The use of a rubber composition for preparing fuel-cell seals

---

JP5844252B2|2016-01-13|Curable resin composition, curable resin composition tablet, molded product, semiconductor package, semiconductor component, and light emitting diode

---

JP6043292B2|2016-12-14|Curable resin composition, curable resin composition tablet, molded product, semiconductor package, semiconductor component, and light emitting diode

---

KR101774306B1|2017-09-04|Polysiloxane composition, hardened material and optical device

---

KR100699741B1|2007-03-27|Thermoplastic elastomer composition for calender-molding and sheets prepared therefrom

---

CN100432137C|2008-11-12|Crosslinkable rubber compositions and uses thereof

---

US20060243947A1|2006-11-02|Curing composition and method for preparing same, light-shielding paste, light-shielding resin and method for producing same, package for light-emitting diode, and semiconductor device

---

EP1958980A1|2008-08-20|Thermoplastic elastomer composition, foam product, and process for production of the composition or foam product

---

KR100700396B1|2007-03-28|Pellet comprising ethylene/?-olefin/non-conjugated polyene copolymer, method for producing thermoplastic elastomer, and method for producing pellet comprising ethylene/?-olefin/non-conjugated polyene copolymer

---

JP2012007002A|2012-01-12|Cycloalkyl group-containing silicone resin composition and usage of the composition

---

KR100734496B1|2007-07-03|Curable composition and uses thereof

---

EP2267071B1|2013-05-01|Rubber composition and use thereof

同族专利:

---

公开号 | 公开日

---

KR100767334B1|2007-10-17|

---

TW583249B|2004-04-11|

---

EP1293534A1|2003-03-19|

---

CN1388813A|2003-01-01|

---

DE60115894D1|2006-01-19|

---

US6743862B2|2004-06-01|

---

EP1293534A4|2003-08-06|

---

WO2001098407A1|2001-12-27|

---

EP1293534B1|2005-12-14|

---

DE60115894T2|2006-08-24|

---

US20030013818A1|2003-01-16|

---

JP5089005B2|2012-12-05|

---

CN1240761C|2006-02-08|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

法律状态:
2000-06-20|Priority to JP2000189745

---

2000-06-20|Priority to JPJP-P-2000-00189745

---

2001-06-19|Application filed by 나까니시 히로유끼, 미쓰이 가가쿠 가부시키가이샤

---

2002-04-04|Publication of KR20020025983A

---

2007-10-17|Application granted

---

2007-10-17|Publication of KR100767334B1

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2000189745|2000-06-20|

---

JPJP-P-2000-00189745|2000-06-20|