Ethylene copolymer composition and its uses

Abstract

To provide an ethylenic copolymer composition that can improve productivity through enhanced adhesion to a fibrous material-containing layer, offering superior bonding strength to the fibrous material-containing layer, without compromising the mechanical properties of the resultant laminate.SOLUTION: The present invention provides an ethylenic copolymer composition that comprises an ethylene α-olefin nonconjugated polyene copolymer (L), satisfying specific requirements, and modified polybutadiene (N), as well as applications thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a crosslinkable ethylene-based copolymer composition, a laminate comprising a layer containing a fibrous material formed using said composition, and uses thereof. [Background Art]

[0002] Ethylene·α-olefin·non-conjugated polyene copolymers such as EPDM are generally excellent in weather resistance, heat resistance and ozone resistance, and are used in automotive industrial parts, industrial rubber products, electrical insulating materials, civil engineering and construction materials, rubberized fabrics and the like.

[0003] Conventional ethylene·α-olefin·non-conjugated polyene copolymers have a disadvantage of inferior adhesion to synthetic fibers compared to polar rubbers such as nitrile rubber, chloroprene rubber and chlorosulfonated polyethylene. As a method for solving this disadvantage, it is disclosed that the adhesion between an ethylene·α-olefin·non-conjugated polyene copolymer and synthetic fibers can be improved by using an adhesion solution of a chlorosulfonated copolymer (Patent Document 1).

[0004] However, today, as environmental issues such as the requirement for non-halogenation have been raised, such adhesion technology that utilizes polarity imparted by halogenation can hardly be said to be optimal. Further, as a conventional adhesion method, a method is known in which synthetic fibers are treated with resorcinol-formaldehyde latex (RFL treatment), then embedded in rubber and crosslinked for adhesion. More specifically, methods using isocyanate or isocyanuric acid derivatives in RFL treatment are known. However, even when these methods are applied to the case where an ethylene·α-olefin·non-conjugated polyene copolymer is used as the rubber, it is difficult to obtain sufficient adhesion.

[0005] Further, in order to improve compression set resistance, it has been proposed to provide a sulfur-vulcanized ethylene propylene rubber compound formed by blending an ethylene·α-olefin·diene copolymer with trans-polyoctenylene rubber and compounded with zinc white (Patent Document 2). [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Special Publication No. 42-23632 [Patent Document 2] Patent No. 2528033 [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of the present invention is to obtain an ethylene copolymer composition that can improve productivity by improving adhesion to a layer containing a fibrous material, has excellent adhesion to a layer containing a fibrous material, and can maintain the mechanical properties of the resulting laminate. [Means for solving the problem]

[0008] The present invention relates to an ethylene-based copolymer composition characterized by comprising the following ethylene-α-olefin-nonconjugated polyene copolymer (L) and the following modified polybutadiene (N). (L) An ethylene-α-olefin-non-conjugated polyene copolymer comprising ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], satisfying the requirements (1) to (4) below. (N) Modified polybutadiene. (1) The molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefins [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. (2) The content of structural units derived from non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of structural units of [A], [B] and [C] being 100 mol%, (3) The Mooney viscosity ML(1+4) at 125°C is 5 to 100. (4) The B value expressed by the following formula (i) is 1.20 or greater. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefins with 4 to 20 carbon atoms [B].] [Effects of the Invention]

[0009] The ethylene copolymer composition of the present invention improves adhesion with a layer containing fibrous material when manufacturing a laminate, thereby increasing the manufacturing speed. Furthermore, the resulting laminate exhibits excellent adhesive strength, making it suitable for a wide range of applications, including hoses and belts. [Modes for carrying out the invention]

[0010] Ethylene-α-olefin-non-conjugated polyene copolymer (L) The ethylene-α-olefin-non-conjugated polyene copolymer (L), which is one of the components constituting the ethylene-based copolymer composition and the layer [I] of the laminate of the present invention, is an ethylene-α-olefin-non-conjugated polyene copolymer that contains structural units derived from ethylene [A], structural units derived from α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C], and satisfies the following requirements (1) to (4). Such a specific ethylene-α-olefin-non-conjugated polyene copolymer is also called an "ethylene-based copolymer (L)" and may be abbreviated as "ethylene-based copolymer (L)".

[0011] Furthermore, one type of α-olefin [B] having 4 to 20 carbon atoms and two or more types of non-conjugated polyene [C] may be used. That is, the ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention contains structural units derived from ethylene [A], structural units derived from at least one type of α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [C]. (1) The molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefin [B] is 40 / 60 to 90 / 10. (2) The content of structural units derived from non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of structural units of [A], [B] and [C] being 100 mol%, (3) The Mooney viscosity ML(1+4) at 125°C is 5 to 100. (4) The B value expressed by the following formula (i) is 1.20 or greater. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the ethylene [A]-α-olefins with 4 to 20 carbon atoms [B] dyad chain fraction.]

[0012] Examples of α-olefins [B] having 4 to 20 carbon atoms include 1-butene (4 carbon atoms), which has a straight chain structure without a side chain, and progresses through 1-nonene (9 carbon atoms) and 1-decene (10 carbon atoms) to 1-nonadecene (19 carbon atoms) and 1-eicosene (20 carbon atoms), as well as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene, which have side chains.

[0013] These α-olefins [B] can be used individually or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferred, with 1-butene, 1-hexene, and 1-octene being particularly preferred, and 1-butene being especially suitable.

[0014] Non-conjugated polyenes [C] specifically include chain-like non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2-norbornene. Examples include cyclic non-conjugated dienes such as rubornene and 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadien.

[0015] These non-conjugated polyenes [C] can be used individually or in combination of two or more. Among these, linear non-conjugated dienes such as 1,4-hexadiene, and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred, with cyclic non-conjugated dienes being preferred, and 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred.

[0016] Examples of the ethylene-based copolymer (L) include the following. Ethylene·1-butene·1,4-hexadiene copolymer, ethylene·1-pentene·1,4-hexadiene copolymer, ethylene·1-hexene·1,4-hexadiene copolymer, ethylene·1-heptene·1,4-hexadiene copolymer, ethylene·1-octene·1,4-hexadiene copolymer, ethylene·1-nonene·1,4-hexadiene copolymer, ethylene·1-decene·1,4-hexadiene copolymer, ethylene·1-butene·1-octene·1,4-hexadiene copolymer, ethylene·1-butene·5-ethylidene-2-norbornene copolymer, ethylene·1-pentene·5-ethylidene-2-norbornene copolymer, ethylene·1-hexene·5-ethylidene-2-norbornene copolymer, ethylene·1-heptene·5-ethylidene-2-norbornene copolymer, ethylene·1-octene·5-ethylidene-2-norbornene copolymer, ethylene·1-nonene·5-ethylidene-2-norbornene copolymer, ethylene·1-decene·5-ethylidene-2-norbornene copolymer, ethylene·1-butene·1-octene·5-ethylidene-2-norbornene copolymer, ethylene·1-butene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-pentene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-hexene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-heptene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-octene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-nonene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, ethylene·1-decene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer, and ethylene·1-butene·1-octene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer. One or two or more types of the ethylene-based copolymer (L) may be used as necessary.

[0017] The ethylene-based copolymer (L) according to the present invention satisfies the following requirements (1) to (4). <<Requirement (1)>> The molar ratio [A] / [B] of a structural unit derived from ethylene [A] to a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms is from 40 / 60 to 90 / 10. The ethylene-based copolymer (L) having a molar ratio within the above range is excellent in the balance between rubber elasticity at low temperatures and tensile strength at room temperatures. The lower limit of [A] / [B] is preferably 45 / 55, more preferably 50 / 50, and particularly preferably 55 / 45. Further, the upper limit of [A] / [B] is preferably 80 / 20, more preferably 75 / 25, and still more preferably 70 / 30.

[0018] <<Requirement (2)>> The content of a structural unit derived from a non-conjugated polyene [C] is 0.1 to 6.0 mol%, where the total of the structural unit derived from [A], the structural unit derived from [B] and the structural unit derived from [C] is 100 mol%. The ethylene-based copolymer (L) having the content within the above range has sufficient crosslinkability and flexibility. The lower limit of the content of the structural unit derived from [C] is preferably 0.5 mol%. The upper limit of the content of the structural unit derived from [C] is preferably 4.0 mol%, more preferably 3.5 mol%, and still more preferably 3.0 mol%. When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, the ethylene-based copolymer (L) having sufficient crosslinkability and flexibility can be obtained.

[0019] <<Requirement (3)>> Mooney viscosity at 125°C, ML(1+4)125°C, is in the range of 5 to 100, preferably 20 to 95, and particularly preferably 50 to 90. When the Mooney viscosity is within the above range, the ethylene-based copolymer (L) has good processability and fluidity, exhibits good post-treatment quality (ribbon handling properties), and the ethylene-based copolymer (L) having excellent physical properties can be obtained.

[0020] Requirements (4) The B value is 1.20 or higher, preferably 1.20 to 1.80, and particularly preferably in the range of 1.22 to 1.40. Ethylene copolymers with a B value of less than 1.20 may exhibit high compression set at low temperatures, potentially resulting in a poor balance between rubber elasticity at low temperatures and tensile strength at room temperature.

[0021] <Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (L)> The ethylene-α-olefin-non-conjugated polyene copolymer (L) according to the present invention can be obtained by various known production methods, for example, by conventionally known production methods using a metallocene catalyst. Examples of metallocene catalysts and production methods using such catalysts can be found in, for example, International Publication No. 2015 / 122415, particularly in paragraphs

[0249] to

[0320] of the said publication.

[0022] Modified polybutadiene (N) The ethylene copolymer composition of the present invention and the modified polybutadiene (N), which is one of the components constituting the ethylene copolymer composition that forms layer [I] of the laminate of the present invention, are polybutadiene modified with an unsaturated carboxylic acid or a derivative thereof. Examples of unsaturated carboxylic acids or their derivatives include unsaturated carboxylic acids or unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and endocis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (nadic acid (trademark)), as well as derivatives thereof such as acid halides, amides, imides, acid anhydrides, and esters. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, maleic acid, nadic acid, and their acid anhydrides are more preferred, and maleic anhydride is particularly preferred. The modified polybutadiene (N) according to the present invention is manufactured and sold by Cray Valley under trade names such as Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon131MA17, Ricon131MA20, and Ricon184MA6, as maleic anhydride modified polybutadiene.

[0023] Transpolyoctenylene (M) Transpolyoctenylene (M), one of the components constituting the ethylene copolymer composition of the present invention and the ethylene copolymer composition forming layer [I] of the laminate of the present invention, is a polymer of octenylene having a trans structure, and is mainly a metathesis polymer of cyclooctene having a trans double bond. The transpolyoctenylene (M) according to the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER.

[0024] <Ethylene copolymer composition> The ethylene copolymer composition of the present invention and the ethylene copolymer composition forming layer [I] of the laminate of the present invention are compositions comprising the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (L) and the above-mentioned modified polybutadiene (N), preferably comprising 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 10 parts by mass of modified polybutadiene (N) per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (L).

[0025] The ethylene copolymer composition of the present invention contains ethylene-α-olefin-non-conjugated polyene copolymer (L) and modified polybutadiene (N), and therefore exhibits good adhesion to layers containing other materials, such as fibrous materials like industrial belts, and the resulting crosslinked laminate has excellent adhesive strength to layers containing fibrous materials.

[0026] The ethylene-based copolymer composition of the present invention preferably contains the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymer (L), the above-mentioned modified polybutadiene (N), and the above-mentioned trans-polyoctenylene (M), which further improves its tackiness and adhesive strength.

[0027] If the ethylene copolymer composition of the present invention contains the above-mentioned transpolyoctenylene (M), it preferably contains 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 10 parts by mass of transpolyoctenylene (M) per 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (L).

[0028] The ethylene copolymer composition of the present invention contains, in addition to ethylene-α-olefin-non-conjugated polyene copolymer (L), trans-polyoctenylene (M) and modified polybutadiene (N), and therefore exhibits good adhesion to layers containing other materials, such as fibrous materials like industrial belts, and the resulting crosslinked laminate has excellent adhesive strength to layers containing fibrous materials.

[0029] The ethylene copolymer composition of the present invention may contain, in addition to the above-mentioned ethylene copolymer (L), transpolyoctenylene (M), and modified polybutadiene (N), other components may be added as needed, within limits that do not impair the effects of the present invention. Other components may include, for example, at least one selected from crosslinking agents, crosslinking aids, vulcanization accelerators, vulcanization aids, fillers, softeners, antioxidants, processing aids, activators, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Furthermore, each additive may be used alone or in combination of two or more.

[0030] <Crosslinking agents, crosslinking aids, vulcanization accelerators, and vulcanization aids> Examples of crosslinking agents commonly used when crosslinking rubber include organic peroxides, phenolic resins, sulfur compounds, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. Of these, organic peroxides and sulfur compounds (hereinafter also referred to as "vulcanizing agents") are preferred.

[0031] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0032] When an organic peroxide is used as a crosslinking agent, the amount of the organic peroxide in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the ethylene copolymer (L). When the amount of organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article, which is preferable.

[0033] When using organic peroxides as crosslinking agents, it is preferable to use crosslinking aids in combination. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; zinc oxide (e.g., ZnO#1, zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.); magnesium oxide; activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0034] When a crosslinking aid is used, the amount of the crosslinking aid in the ethylene copolymer composition is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 6 moles, per mole of organic peroxide.

[0035] Examples of sulfur compounds (vulcanizing agents) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

[0036] When a sulfur-based compound is used as a crosslinking agent, the amount of the sulfur-based compound in the copolymer composition is usually 0.1 to 10 parts by mass, preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, per 100 parts by mass of the ethylene copolymer (L). When the amount of the sulfur-based compound is within the above range, there is no bloom on the surface of the resulting molded article, and the ethylene copolymer composition exhibits excellent crosslinking properties.

[0037] When using sulfur-based compounds as crosslinking agents, it is preferable to use vulcanization accelerators in combination. Examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Sunceller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noxellar MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-di Thiazole-based vulcanization accelerators such as ethyl-4-morpholinothio)benzothiazole and dibenzothiadyl disulfide (e.g., Suncellar DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorthotrylguanidine; aldehydeamine-based vulcanization accelerators such as acetaldehyde-aniline condensate and butyraldehyde-aniline condensate; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (e.g., Suncellar DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); Thiuram-based vulcanization accelerators such as Ra TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), tetramethyl thiuram disulfide (e.g., Suncellar TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethyl thiuram disulfide (e.g., Suncellar TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutyl thiuram disulfide (e.g., Suncellar TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), and dipentamethylenethiuram tetrasulfide (e.g., Suncellar TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of dithioate-based vulcanization accelerators include zinc carbamate, zinc dibutyldithiocarbamate (e.g., Suncellar PZ, Suncellar BZ, and Suncellar EZ (product names; manufactured by Sanshin Chemical Industry Co., Ltd.)), and tellurium diethyldithiocarbamate; thiourea-based vulcanization accelerators include ethylenethiourea (e.g., Suncellar BUR (product name; manufactured by Sanshin Chemical Industry Co., Ltd.), Suncellar 22-C (product name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea); and xantate-based vulcanization accelerators such as zinc dibutylxatonate.

[0038] When using vulcanization accelerators, the amount of these vulcanization accelerators in the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of ethylene-based copolymer (L). When the amount of vulcanization accelerator is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article. When using sulfur-based compounds as crosslinking agents, vulcanization aids can be used in combination.

[0039] Examples of vulcanization aids include zinc oxide (e.g., ZnO#1, two types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)). When a vulcanization aid is used, the amount of the vulcanization aid in the ethylene copolymer composition is usually 1 to 20 parts by mass per 100 parts by mass of the ethylene copolymer (L).

[0040] <Filler> The filler constituting the ethylene copolymer composition of the present invention is a known rubber reinforcing agent blended into a rubber composition, and is an inorganic substance commonly referred to as carbon black or an inorganic reinforcing agent.

[0041] Specifically, fillers related to the present invention include Asahi #55G, Asahi #60UG (both manufactured by Asahi Carbon Co., Ltd.), Seast (V, SO, 116, 3, 6, 9, SP, TA, etc.) carbon black (manufactured by Tokai Carbon Co., Ltd.), carbon blacks surface-treated with silane coupling agents, etc., and silica, activated calcium carbonate, fine talc, fine silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

[0042] These fillers may be used individually or as a mixture of two or more. Preferably, the fillers used in this invention are carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

[0043] If the copolymer composition of the present invention contains a filler, it should be blended in an amount of 50 to 300 parts by mass, preferably 80 to 250 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0044] <Softener> Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softening agents such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factis). Of these, petroleum-based softening agents are preferred, and process oil is particularly preferred.

[0045] When an ethylene copolymer composition contains a softening agent, the amount of softening agent is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0046] <Anti-aging agent (stabilizer)> By incorporating an antioxidant (stabilizer) into the ethylene copolymer composition of the present invention, the lifespan of the seal packing formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0047] Examples of anti-aging agents include aromatic 2-amine anti-aging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether anti-aging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate anti-aging agents such as dibutyldithiocarbamate nickel; and sulfur-based anti-aging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0048] When the ethylene copolymer composition contains an antioxidant, the amount of the antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of the ethylene copolymer (L). When the amount of the antioxidant is within the above range, bloom is not present on the surface of the resulting molded article, and the occurrence of vulcanization inhibition can be suppressed.

[0049] <Processing aids> As processing aids, those commonly used in rubber processing can be widely used. Specifically, examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. Of these, stearic acid is preferred.

[0050] If the copolymer composition contains a processing aid, it can be appropriately blended in an amount of typically 1 to 3 parts by mass per 100 parts by mass of the ethylene copolymer (L). When the amount of processing aid is within the above range, it is preferable because it provides excellent processability such as kneadability, extrusionability, and injection moldability. The processing aid may be a single type or two or more types.

[0051] <Activating agent> Examples of activators include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl merilate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide moduloides; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0052] If the copolymer composition contains an activator, the amount of activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the ethylene copolymer (L).

[0053] <Laminate> The laminate of the present invention is a laminate in which a layer [I] made of the ethylene copolymer composition of the present invention and a layer [II] containing a fibrous material are in contact.

[0054] [I] Layer consisting of an ethylene copolymer composition The layer [I] constituting the laminate of the present invention is a layer formed by crosslinking the above-mentioned ethylene copolymer composition.

[0055] 《Layer containing fibrous material[II]》 The layer [II] constituting the laminate of the present invention contains a fibrous material, and at least a portion of the layer contains the fibrous material.

[0056] <Textile materials> Examples of fibrous materials that form layer [II] according to the present invention include various known fibrous materials, such as natural fibers like cotton and wood cellulose fibers; organic fibrous materials made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, poly(p-phenylenebenzobisoxazole), polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fibrous materials such as glass fibers, PAN-based carbon fibers, pitch-based carbon fibers, alumina fibers, silicon carbide fibers, aluminum borate fibers, and potassium titanate whiskers.

[0057] These fibrous materials may be long fibers (filaments) or short fibers (staples). Furthermore, the fibrous materials may be corded yarn, spun yarn, woven fabric, knitted fabric, canvas, nonwoven fabric, etc.

[0058] Examples of the polyamides mentioned above include aliphatic polyamides such as nylon 6, nylon 6,6, and nylon 6,10; semi-aromatic polyamides such as polymetaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), or copolymer polyamides containing these units; and fully aromatic polyamides such as polybenzamide, polypphenylene terephthalamide, and polymphenylene isophthalamide.

[0059] Furthermore, these fibrous materials may be surface-treated by known methods such as RFL treatment in order to improve their adhesion to each other or to the layer [I] made of the ethylene copolymer composition.

[0060] <RFL processing> RFL treatment involves bonding fibrous materials using a treatment solution (RFL solution) containing resorcinol, formalin, and latex. This RFL solution is a mixture of the initial condensate of resorcinol and formalin and rubber latex. As rubber latex, styrene-butadiene-vinylpyridine terpolymer (VP), styrene-butadiene copolymer (SBR), chloroprene (CR), acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR (H-NBR), chlorosulfonated ethylene (CSM), and natural rubber can be used. These can be used individually or blended in combination of two or more types.

[0061] <Method for manufacturing laminates> Various known methods for manufacturing laminates can be employed to produce the laminate of the present invention. For example, various known methods can be employed, such as laminating a layer [I] made of an uncrosslinked ethylene copolymer composition, which has been manufactured (molded) in advance by a known method, with a layer [II] containing a fiber material, and then crosslinking the layer [I] made of the ethylene copolymer composition; laminating a crosslinked layer [I] made of the ethylene copolymer composition with a layer [II] containing a fiber material; or extruding a layer [I] made of the ethylene copolymer composition onto a layer [II] containing a fiber material, and then crosslinking the layer [I] made of the ethylene copolymer composition.

[0062] The above ethylene copolymer composition is obtained by kneading the above ethylene-α-olefin-non-conjugated polyene copolymer (L), the above trans-polyoctenylene (M), and the above modified polybutadiene (N), along with a crosslinking agent and, if necessary, additives such as fillers, softeners, antioxidants, and processing aids, using various known kneading and mixing equipment, such as Banbury mixers, kneaders, internal mixers (closed mixers) like Intermix, and rolls.

[0063] The uncrosslinked ethylene copolymer composition obtained by kneading may be molded into the desired shape using various molding methods such as an extruder, calender roll, press, injection molding machine, or transfer molding machine, and then crosslinked to form a layer [I] made of the ethylene copolymer composition, which is then laminated (bonded) with a layer [II] containing fiber material. Alternatively, the uncrosslinked ethylene copolymer composition may be molded into the desired shape using the above method, and then laminated (bonded) with a layer [II] containing fiber material and crosslinked.

[0064] The method for crosslinking the layer [I] made of an ethylene copolymer composition may be either a method of heating with a crosslinking agent, or a method of irradiation with light, gamma rays, or electron beams.

[0065] Furthermore, when crosslinking, a mold may be used, or the crosslinking may be carried out without using a mold. If a mold is not used, the molding and crosslinking processes are usually carried out continuously. As for heating methods in the crosslinking tank, heating tanks such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), and steam can be used.

[0066] Applications of laminates A laminate comprising a layer [I] made of the ethylene copolymer composition of the present invention and a layer [II] containing a fibrous material in contact with each other is suitably used for automobile hoses, water supply hoses, gas hoses; industrial belts such as power transmission belts and conveyor belts; and escalator handrails.

[0067] Examples of automotive hoses include brake hoses, radiator hoses, heater hoses, and air cleaner hoses. Examples of the above-mentioned power transmission belts include V-belts, flat belts, and toothed belts. Examples of the above-mentioned conveying belts include light conveying belts, cylindrical belts, rough-top belts, flanged conveying belts, U-shaped guided conveying belts, and V-guided conveying belts. [Examples]

[0068] The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. The ethylene-α-olefin-nonconjugated polyene copolymer (L) used in the examples of the present invention is shown below.

[0069] [Ethylene-α-olefin-nonconjugated polyene copolymer] Following the description in [Synthesis Example C1] of International Publication No. 2015 / 122415, an ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer having the following properties was obtained. Hereinafter, this will be referred to as "ethylene-based copolymer (L-1)". The composition and properties of the ethylene copolymer (L-1) are as follows: Ethylene-derived structural units: 67.7 mol% Structural units derived from 1-butene: 30.0 mol% Structural units derived from ENB: 2.3 mol% Mooney viscosity ML (1+4) 100℃: 30 Mooney viscosity ML (1+4) 125℃: 22 B value: 1.3

[0070] [Physical properties of ethylene copolymer (L-1)] <Molar amounts of structural units derived from ethylene, structural units derived from α-olefins, and structural units derived from non-conjugated polyenes> The aforementioned molar amount is 1 The intensity was determined by measuring it using an H-NMR spectrometer. Details of the measurement conditions are described in International Publication No. 2015 / 122415.

[0071] <Mooney viscosity> Mooney viscosity (ML(1+4) at 100°C and 125°C) was measured using a Mooney viscometer (SMV202 model, Shimadzu Corporation) in accordance with JIS K6300 (1994).

[0072] Using o-dichlorobenzene-d4 / benzene-d6 (4 / 1 [v / v]) as the measurement solvent, at a measurement temperature of 120°C,13 The 1C-NMR spectrum (100 MHz, JEOL ECX400P) was measured and calculated based on the following formula (i). B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) [Here, [E], [X], and [Y] represent the mole fractions of structural units derived from ethylene [A1], α-olefins with 4 to 20 carbon atoms [A2], and non-conjugated polyenes [A3], respectively, and [EX] represents the ethylene [A1]-α-olefins with 4 to 20 carbon atoms [A2] dyad chain fraction.]

[0073] The ethylene-α-olefin-nonconjugated polyene copolymers used in the comparative examples of the present invention are shown below.

[0074] [Ethylene-α-olefin-nonconjugated polyene copolymer] As the ethylene-α-olefin-non-conjugated polyene copolymer, the following ethylene-propylene-ENB copolymer (copolymer-2) was used. Ethylene-propylene-ENB copolymer Product name: Mitsui EPT 4045M: Mooney viscosity ML(1+4) 100℃ = 45, ethylene content = 45 wt%, diene (ENB) content = 7.6 wt%.

[0075] [Modified polybutadiene (N)] As the modified polybutadiene (N), we used maleic anhydride-modified polybutadiene (N-1) from Ricon131MA17 [trade name: Cray Valley].

[0076] [Transpolyoctenylene (M)] Transpolyoctenylene (M) was used, specifically the product name Vestenamer 8012 from Evonik Industries.

[0077] Properties of Ethylene-Based Copolymer Compositions (Non-Crosslinked Materials) <Measurement of adhesiveness> Using a probe tack tester, the tackiness (Peak Value (gf)) was evaluated under the following conditions. Using an uncrosslinked sheet with a thickness of 1 mm, 5mm diameter stainless steel probe Approach speed: 120mm / min. Pressure: 100g Pressurization time: 20 seconds. Peeling speed: 120mm / min. The temperature at which the probe and test specimen (uncrosslinked sheet) were placed was measured at 50°C.

[0078] Properties of crosslinked ethylene copolymer compositions <Tear strength> In accordance with JIS K6252, measurements were taken using a sheet with a thickness of 2 mm after crosslinking, with an angle-shaped dumbbell test specimen without cuts, at a tensile speed of 500 mm / min.

[0079] <Durometer A hardness> In accordance with JIS K 6253, the hardness of the sheets (Type A durometer, HA) was measured using six 2mm thick sheet-like crosslinked material with smooth surfaces, stacked with the flat portions facing each other to a thickness of approximately 12mm. However, test specimens containing foreign matter, air bubbles, or scratches were not used. Furthermore, the dimensions of the measurement surface of the test specimen were such that measurement could be taken with the indenter tip at a distance of 12mm or more from the edge of the specimen.

[0080] <Tensile stress at fracture, tensile elongation at fracture> The tensile stress and elongation at the tensile fracture point of the sheet were measured using the following method. A dumbbell-shaped test specimen of type 3, as described in JIS K 6251 (1993), was prepared by punching out sheets. Using this specimen, a tensile test was performed under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min., according to the method specified in Section 3 of JIS K6251, and the tensile stress at fracture (TB) and tensile elongation at fracture (EB) were measured.

[0081] <Peel strength> The peel strength (adhesion strength) between a layer [I] consisting of a crosslinked ethylene copolymer composition and a layer [II] containing fibrous material was determined by the following method.

[0082] A 3mm thick uncrosslinked sheet was placed on a nylon fiber woven fabric [manufactured by Ayaha Kogyo Co., Ltd.] treated with RFL, and the uncrosslinked sheet was crosslinked using a 200-ton press molding machine at 170°C for 15 minutes to obtain a laminate. A 25mm wide test piece was punched out from the laminate, and a T-peel test was performed at a tensile speed of 50mm / min. to determine the peel strength (adhesion strength) (N / cm). The peel test was performed three times, and the average value was taken as the peel strength.

[0083] [Example 1] The ethylene copolymer (L-1) was kneaded for 30 seconds. To 100 parts by weight of the kneaded ethylene copolymer (L-1), 5 parts by weight of zinc oxide (ZnO#1) was added as a crosslinking aid, 1 part by weight of stearic acid as a lubricant, 2 parts by weight of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane (product name Irganox 1010, manufactured by BASFF Japan Co., Ltd.) as an antioxidant, 4 parts by weight of 2-mercaptobenzimidazole (product name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.), 40 parts by weight of carbon black (manufactured by Asahi Carbon Co., Ltd., product name Asahi #70), 10 parts by weight of silica (manufactured by Evonik, product name ULTRASIL VN2), and a softener (product name Diana Process Oil PW-380) Ten parts by mass of [manufactured by Idemitsu Kosan Co., Ltd.] and five parts by mass of transpolyoctenylene (M) from Evonik Industries, trade name: VESTENAMER 8012, were mixed for 2 minutes in a 1.7-liter Banbury mixer [manufactured by Kobe Steel, Ltd.]. The ram was then raised and cleaned, and the mixture was mixed for another minute. The mixture was then discharged at approximately 150°C to obtain formulation (Formulation-1). This mixing was carried out at a packing density of 70%.

[0084] Next, 172 parts by weight of this mixture was wound onto an 8-inch roll (front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and 6.8 parts by weight of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., trade name Mitsui DCP-40C) and 5 parts by weight of Ricon131MA17 were added as crosslinking agents. The mixture was kneaded for 10 minutes to obtain mixture (mixture-2). Then, according to the test specimens, each mixture was divided into sheets to prepare uncrosslinked sheets with thicknesses of 1 mm, 2 mm, and 3 mm.

[0085] The tackiness (gf) of the obtained 1 mm thick uncrosslinked sheet was measured using the method described above. The results are shown in Table 1. Furthermore, the obtained 2 mm thick uncrosslinked sheet was pressed at 170°C for 15 minutes using a 100-ton press molding machine to produce a crosslinked sheet. The physical properties of the obtained crosslinked sheet were measured using the method described above. The results are shown in Table 1.

[0086] [Comparative Example 1] Except for using copolymer-2 instead of copolymer (L-1) used in Example 1, and changing the type and amount of compounding agents (additives) to those shown in Table 1, an uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained using the method described above, and their physical properties were evaluated. The results are shown in Table 1.

[0087] [Comparative Example 2] Except for not using VESTENAMER 8012 and silica as used in Example 1, an uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained by the method described in Example 1, and their physical properties were evaluated by the method described above. The results are shown in Table 1.

[0088] [Table 1]

Claims

1. An ethylene-based copolymer composition characterized by containing the following ethylene-α-olefin-non-conjugated polyene copolymer (L) and the following modified polybutadiene (N). (L) An ethylene-α-olefin-non-conjugated polyene copolymer comprising ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], satisfying the requirements of (1) to (4) below. (N) Modified polybutadiene. (1) The molar ratio [[A] / [B]] of structural units derived from ethylene [A] to structural units derived from α-olefins [B] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. (2) The content of structural units derived from non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of structural units of [A], [B] and [C] being 100 mol%, (3) The Mooney viscosity ML(1+4) at 125°C is 5 to 100. (4) The B value expressed by the following formula (i) is 1.20 or higher. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) [Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefins with 4 to 20 carbon atoms [B], and unconjugated polyenes [C], respectively, and [EX] represents the dyad chain fraction of ethylene [A]-α-olefins with 4 to 20 carbon atoms [B].]

2. The ethylene-based copolymer composition according to claim 1, wherein the 4- to 20 carbon atom α-olefin [B] constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) is 1-butene.

3. The ethylene-based copolymer composition according to claim 1, comprising 0.5 to 50 parts by mass of modified polybutadiene (N) per 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (L).

4. The ethylene copolymer composition according to claim 1, characterized in that the ethylene copolymer composition further comprises (M) transpolyoctenylene.

5. The ethylene-based copolymer composition according to claim 4, comprising 0.5 to 50 parts by mass of transpolyoctenylene (M) per 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (L).

6. The ethylene copolymer composition according to claim 1, characterized in that the ethylene copolymer composition further comprises (B) an organic peroxide as a crosslinking agent.

7. A laminate characterized in that a layer [I] made of an ethylene copolymer composition according to any one of claims 1 to 6 is in contact with a layer [II] containing a fibrous material.

8. The laminate according to claim 7, wherein an ethylene copolymer composition is crosslinked.

9. The laminate according to claim 7, wherein the fibrous material of the above layer [II] includes RFL-treated fibers.

10. The laminate according to claim 7, wherein the fibrous material of the above layer [II] is canvas.

11. An industrial belt having the laminate described in claim 7.

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