JP2024073051A - Ethylenic copolymer composition and applications thereof - Google Patents

Abstract

To provide an ethylenic copolymer composition that improves stickiness to layers containing textile material, leading to improved productivity, and also enhances adhesiveness to layers containing textile material, while maintaining the mechanical properties of resultant laminates.SOLUTION: The present invention provides an ethylenic copolymer composition comprising an ethylene α-olefin nonconjugated polyene copolymer (L) that satisfies specific requirements, trans-polyoctenylene (M), and a specific amount of aging resister (F) and applications thereof.SELECTED DRAWING: None

Description

The present invention relates to a crosslinkable ethylene copolymer composition, a laminate using said composition with a layer containing a fiber material, and uses thereof.

Ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM generally have excellent weather resistance, heat resistance, and ozone resistance, and are used in industrial automotive parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubberized fabrics, etc.

Conventional ethylene-α-olefin-non-conjugated polyene copolymers have the disadvantage of having inferior adhesion to synthetic fibers compared to polar rubbers such as nitrile rubber, chloroprene rubber, and chlorosulfonated polyethylene. As a method to solve this disadvantage, it has been disclosed that an adhesive solution of a chlorosulfonated copolymer is used to improve the adhesion between ethylene-α-olefin-non-conjugated polyene copolymer and synthetic fibers (Patent Document 1).

However, in today's world where environmental issues such as non-halogenation are a concern, it is difficult to say that such adhesive technology that utilizes the polarity of halogenation is optimal. Also, a conventional adhesive method is known in which synthetic fibers are treated with resorcinol formaldehyde latex (RFL treatment), then embedded in rubber and cross-linked to bond. More specifically, a method is known in which isocyanate or isocyanuric acid derivatives are used in the RFL treatment. However, even if these methods are applied when ethylene-α-olefin-non-conjugated polyene copolymer is used as the rubber, it is difficult to obtain sufficient adhesion.

In addition, in order to improve compression set resistance, it has been proposed to compound a sulfur-vulcanized ethylene propylene rubber compound in which zinc oxide made by compounding ethylene-α-olefin-diene copolymer with trans-polyoctenylene rubber is compounded (Patent Document 2).

Japanese Patent Publication No. 42-23632 Japanese Patent No. 2528033

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 fiber material, has good heat aging resistance, and has excellent adhesion to a layer containing a fiber material.

The present invention relates to an ethylene-based copolymer composition comprising the following ethylene/α-olefin/non-conjugated polyene copolymer (L), the following trans-polyoctenylene (M), and a specific amount of the following antioxidant (F).
(L) An ethylene/α-olefin/non-conjugated polyene copolymer containing a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], which satisfies the following requirements (1) to (4):
(M) trans polyoctenylene.
The antioxidant (F) is contained in an amount of 8 to 24 parts by mass per 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (L).
(1) the molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] to the structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms is 40/60 to 90/10;
(2) the content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B] and [C];
(3) Mooney viscosity ML(1+4)125°C at 125°C is 5 to 100,
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2[Y]) / (2 x [E] x ([X] + [Y])) (i)
[Here, [E], [X] and [Y] respectively represent the molar fractions of ethylene [A], the α-olefin [B] having 4 to 20 carbon atoms, and the non-conjugated polyene [C], and [EX] represents the dyad chain fraction of ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms.]

The ethylene copolymer composition of the present invention contains a relatively large amount of antioxidant (F), which significantly improves adhesion, making it possible to increase the production speed when producing a laminate with a layer containing a fiber material. In addition, the laminate obtained by crosslinking has excellent adhesive strength, making it suitable for a wide range of uses, including hoses, belts, etc.

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

The α-olefin [B] having 4 to 20 carbon atoms and the non-conjugated polyene [C] may each be used alone or in combination of two or more kinds. That is, the ethylene/α-olefin/non-conjugated polyene copolymer (L) according to the present invention contains a structural unit derived from ethylene [A], a structural unit derived from at least one kind of α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from at least one kind of non-conjugated polyene [C].
(1) the molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] to the structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms is 40/60 to 90/10;
(2) the content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B] and [C];
(3) Mooney viscosity ML(1+4)125°C at 125°C is 5 to 100,
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2[Y]) / [2 x [E] x ([X] + [Y])] (i)
[Here, [E], [X] and [Y] respectively represent the molar fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], and [EX] represents the ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms dyad chain fraction.]

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

These α-olefins [B] can be used alone 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 particularly preferred.

Specific examples of non-conjugated polyenes [C] include linear 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. cyclic non-conjugated dienes such as norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene; 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-nonadiene.

These non-conjugated polyenes [C] may be used alone or in combination of two or more kinds.
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, and among these, cyclic non-conjugated dienes are preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred.

Examples of the ethylene 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 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; ethylene/1-butene/1-octene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer.
The ethylene copolymer (L) may be used alone or in combination of two or more, as required.

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

<Requirement (2)>
The ethylene-based copolymer (L) has a content ratio of the structural unit derived from the non-conjugated polyene [C] of 0.1 to 6.0 mol %, relative to 100 mol % of the total of the structural units derived from the [A], the structural units derived from the [B], and the structural units derived from the [C]. The ethylene-based copolymer (L) having this content ratio in 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 even more preferably 3.0 mol %.
When the content of the structural unit derived from the non-conjugated polyene [C] is within the above range, an ethylene copolymer (L) having sufficient crosslinkability and flexibility can be obtained.

<Requirement (3)>
The Mooney viscosity ML(1+4)125° C. is in the range of 5-100, preferably 20-95, and particularly preferably 50-90.
When the Mooney viscosity is within the above range, the ethylene-based copolymer (L) has good processability and flowability, and exhibits good post-treatment quality (ribbon handling property) and has excellent physical properties.

<Requirement (4)>
The B value is 1.20 or more, preferably 1.20 to 1.80, and particularly preferably 1.22 to 1.40.
An ethylene copolymer having a B value of less than 1.20 has a large compression set at low temperatures, and there is a risk that an ethylene copolymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature cannot be obtained.

<<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, a conventionally known production method using a metallocene catalyst. As the metallocene catalyst and the production method using the catalyst, for example, the examples described in WO 2015/122415, particularly paragraphs [0249] to [0320] of the publication, can be adopted.

<<Trans-polyoctenylene (M)>>
Trans-polyoctenylene (M), which is one of the components constituting the ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition that forms the 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 ethylene copolymer composition of the present invention contains the trans-polyoctenylene (M), and thus the compatibility with fibrous materials is improved, thereby improving the tackiness and adhesion to the fibrous materials.
The trans-polyoctenylene (M) according to the present invention is manufactured and sold by Evonik Industries under the trade name VESTENAMER.

<<Anti-aging agent (F)>>
The antioxidant used in the present invention may be any known antioxidant, such as an amine-based antioxidant, a phenol-based antioxidant, or a sulfur-based antioxidant.

Examples of the antiaging agent include aromatic secondary amine-based antiaging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenol-based antiaging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether-based antiaging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antiaging agents such as nickel dibutyldithiocarbamate; and sulfur-based antiaging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.
The antioxidant (F) is not limited to one type, and two or more types can be used.

The ethylene copolymer composition of the present invention contains a specific amount of antioxidant (F), which significantly improves adhesion. This allows for faster production of a laminate with a layer containing a fiber material, and the adhesive strength of the laminate obtained by crosslinking is also excellent.

<Ethylene-Based Copolymer Composition>
The ethylene-based copolymer composition of the present invention and the ethylene-based copolymer composition forming the layer [I] of the laminate of the present invention are compositions containing the ethylene-α-olefin-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the antioxidant (F) in amounts of 8 to 24 parts by mass, preferably 8 to 20 parts by mass, and more preferably 8 to 16 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L), and preferably contain 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 the trans-polyoctenylene (M) per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (L).

The ethylene copolymer composition of the present invention contains trans-polyoctenylene (M) and a specific amount of antioxidant (F) in addition to ethylene-α-olefin-non-conjugated polyene copolymer (L), so that the adhesiveness to other materials, for example layers containing fibrous materials such as industrial belts, is significantly improved, and the crosslinked laminate also has superior adhesive strength to layers containing fibrous materials.

In addition to the ethylene copolymer (L), trans-polyoctenylene (M) and antioxidant (F), the ethylene copolymer composition of the present invention can contain other components according to the desired purpose within a range that does not impair the effects of the present invention. The other components may contain at least one selected from, for example, a crosslinking agent, a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a filler, a softener, an antioxidant, a processing aid, an activator, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant and a thickener. Each additive may be used alone or in combination of two or more.

<Crosslinking Agent, Crosslinking Coagent, Vulcanization Accelerator, and Vulcanization Coagent>
Examples of the crosslinking agent include crosslinking agents generally used when crosslinking rubber, such as organic peroxides, phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinones or derivatives thereof, amine-based compounds, azo-based compounds, epoxy-based compounds, isocyanate-based compounds, etc. Among these, organic peroxides and sulfur-based compounds (hereinafter also referred to as "vulcanizing agents") are preferred.

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)hexyne-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.

When an organic peroxide is used as the 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-based copolymer (L). When the amount of the organic peroxide is within the above range, the ethylene-based copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the resulting molded article, which is preferable.

When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking assistant in combination. Examples of crosslinking assistants include sulfur; quinone dioxime crosslinking assistants such as p-quinone dioxime; acrylic crosslinking assistants such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking assistants such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking assistants; divinylbenzene; and metal oxides such as zinc oxide (e.g., ZnO#1 and zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Seki Kogyo Co., Ltd.)).

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.

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

When a sulfur-based compound is used as the 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-based copolymer (L). When the amount of the sulfur-based compound is within the above range, there is no bloom on the surface of the obtained molded article, and the ethylene-based copolymer composition exhibits excellent crosslinking properties.

When a sulfur-based compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination.
Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N'-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (e.g., Suncerer M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noccelaer MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-dinitrophenyl)mercaptobenzothiazole, Thiazole-based vulcanization accelerators such as ethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (for example, Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenyl guanidine, triphenyl guanidine and diorthotolyl guanidine; aldehyde amine-based vulcanization accelerators such as acetaldehyde-aniline condensate and butyraldehyde-aniline condensate; imidazoline-based vulcanization accelerators such as 2-mercaptoimidazoline; tetramethylthiuram monosulfide (for example, Sancerer DM (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (e.g., Sancerer TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (e.g., Sancerer TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (e.g., Sancerer TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutylthiuram disulfide (e.g., Sancerer TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and dipentamethylenethiuram tetrasulfide (e.g., Sancerer TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); zinc dimethyldithiocarbamate, diethyldithio Examples of the vulcanization accelerator include dithioacid salt vulcanization accelerators such as zinc carbamate, zinc dibutyldithiocarbamate (for example, Sanseller PZ, Sanseller BZ, and Sanseller EZ (trade names; manufactured by Sanshin Chemical Industry Co., Ltd.)) and tellurium diethyldithiocarbamate; thiourea vulcanization accelerators such as ethylenethiourea (for example, Sanseller BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sanseller 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N,N'-diethylthiourea, and N,N'-dibutylthiourea; and xanthate vulcanization accelerators such as zinc dibutylxatogenate.

When a vulcanization accelerator is used, the blending amount of the vulcanization accelerator 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-based copolymer (L). When the blending amount of the vulcanization accelerator is within the above range, the copolymer composition exhibits excellent crosslinking properties without blooming on the surface of the obtained molded article. When a sulfur-based compound is used as the crosslinking agent, a vulcanization assistant can be used in combination.

Examples of the vulcanization aid include zinc oxide (e.g., ZnO#1 and zinc oxide type 2, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and activated zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Seki Kogyo Co., Ltd.)).
When a vulcanization aid is used, the blending amount of the vulcanization aid in the ethylene copolymer composition is usually 1 to 20 parts by mass based on 100 parts by mass of the ethylene copolymer (L).

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 usually an inorganic substance called carbon black or an inorganic reinforcing agent.

Specific examples of fillers that may be used in the present invention include Asahi #55G and 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.), these carbon blacks that have been surface-treated with a silane coupling agent, etc., as well as silica, activated calcium carbonate, fine powdered talc, fine powdered silicic acid, light calcium carbonate, heavy calcium carbonate, talc, clay, etc.

These fillers may be used alone or in combination of two or more.
As the filler in the present invention, preferably used are carbon black, silica, light calcium carbonate, heavy calcium carbonate, talc, clay, and the like.

When the copolymer composition of the present invention contains a filler, it is usually 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).

<Softener>
Examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners 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 derivatives thereof; synthetic polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub (factice). Of these, petroleum-based softeners are preferred, and process oil is particularly preferred.

When the ethylene-based copolymer composition contains a softener, the amount of the softener is generally 2 to 100 parts by mass, and preferably 10 to 100 parts by mass, per 100 parts by mass of the ethylene-based copolymer (L).

<Processing aids>
As the processing aid, a wide variety of processing aids that are generally compounded with rubber can be used.Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, and esters.Of these, stearic acid is preferred.

When the copolymer composition contains a processing aid, it can be appropriately blended in an amount of usually 1 to 3 parts by mass per 100 parts by mass of the ethylene copolymer (L). When the blending amount of the processing aid is within the above range, it is preferable since the processability such as kneading processability, extrusion processability, and injection moldability is excellent.
The processing aid may be used alone or in combination with two or more kinds.

<Activator>
Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl methylate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

When the copolymer composition contains an activator, the amount of the 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).

<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 is in contact with a layer [II] containing a fiber material.

<<Layer [I] made of ethylene-based copolymer composition>>
The layer [I] made of an ethylene-based copolymer composition constituting the laminate of the present invention is preferably a layer obtained by crosslinking the above-mentioned ethylene-based copolymer composition.

<<Layer containing fiber material [II]>>
The layer [II] containing a fiber material that constitutes the laminate of the present invention contains a fiber material in at least a part of the layer.

<Textile materials>
Examples of fiber materials forming the layer [II] according to the present invention include various known fiber materials, for example, natural fibers such as cotton and wood cellulose fibers; organic fiber materials such as fibers made of synthetic resins such as polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, polyether ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymers; and inorganic fiber 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.

These fiber materials may be long fibers (filaments) or short fibers (staples). The fiber materials may also be cord yarns, spun yarns, woven fabrics, knitted fabrics, canvas, nonwoven fabrics, etc.

The above polyamides 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, poly-p-phenylene terephthalamide, and poly-m-phenylene isophthalamide.

These fiber materials may be surface-treated by a known method such as RFL treatment to improve adhesion between the fiber materials themselves or between the fiber materials and the layer [I] made of the ethylene copolymer composition.

<RFL Processing>
The RFL treatment is a process for adhesively treating a fiber material using a treatment liquid (RFL liquid) containing resorcin, formalin, and latex of the fiber material, and this RFL liquid is a mixture of an initial condensate of resorcin and formalin and rubber latex. As the rubber latex, styrene-butadiene-vinylpyridine terpolymer (VP), styrene-butadiene copolymer (SBR), chloroprene (CR), acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR (H-NBR), chlorosulfonated ethylene (CSM), natural rubber, etc. can be used, and these can be used alone or in a blend of two or more types.

<Method of manufacturing laminate>
To produce the laminate of the present invention, various known methods for producing laminates can be used. For example,
A layer [I] made of an uncrosslinked ethylene copolymer composition produced (molded) in advance by a known method
a method of laminating a layer [I] made of an ethylene-based copolymer composition and a layer [II] containing a fiber material together, a method of crosslinking the layer [I] made of an uncrosslinked or crosslinked ethylene-based copolymer composition and a layer [II] containing a fiber material together, a method of extrusion coating the layer [I] made of an ethylene-based copolymer composition on the layer [II] containing a fiber material, or a method of extrusion coating and then crosslinking the layer [I] made of an ethylene-based copolymer composition.
The layer [I] made of the ethylene copolymer composition can be produced by various known methods.

The ethylene copolymer composition can be obtained by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (L), the trans-polyoctenylene (M), and the antioxidant (F), as well as a crosslinking agent and, if necessary, additives such as a filler, a softener, an antioxidant, and a processing aid, using various known kneading and mixing devices, for example, a Banbury mixer, a kneader, an internal mixer (internal mixer) such as an intermix, and a roll.

The uncrosslinked ethylene copolymer composition obtained by kneading may be molded into an intended shape by various molding methods such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine, and then crosslinked to form a layer [I] made of the ethylene copolymer composition, which may then be laminated (bonded) with a layer [II] containing a fiber material, or the uncrosslinked ethylene copolymer composition may be molded into an intended shape by the above-mentioned method, and then laminated (bonded) with a layer [II] containing a fiber material, thereby crosslinking the composition.

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

When crosslinking, a mold may be used, or crosslinking may be performed without a mold. When a mold is not used, the molding and crosslinking steps are usually performed continuously. Heating methods in the crosslinking tank include hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic waves), steam, and other heating tanks.

<<Applications of the laminate>>
A laminate in which a layer [I] made of the ethylene-based copolymer composition of the present invention is in contact with a layer [II] containing a fiber material is suitably used for automobile hoses, water supply hoses, and gas hoses; industrial belts such as transmission belts and conveyor belts; and escalator handrails.

Examples of the automobile hose include brake hoses, radiator hoses, heater hoses, and air cleaner hoses.
Examples of the transmission belt include a V-belt, a flat belt, a toothed belt, etc. Examples of the conveyor belt include a light conveyor belt, a cylindrical belt, a rough top belt, a conveyor belt with a flange, a conveyor belt with a U-shaped guide, a conveyor belt with a V-guide, etc.

The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these.
The ethylene/α-olefin/non-conjugated polyene copolymer (L) used in the examples of the present invention is shown below.

[Ethylene-α-olefin-non-conjugated polyene copolymer]
According to the description of [Synthesis Example C1] of WO 2015/122415, an ethylene-1-butene-5-ethylidene-2-norbornene (ENB) copolymer having the following physical properties was obtained. Hereinafter, this is referred to as "ethylene copolymer (L-1)".
The constitution and physical properties of the ethylene copolymer (L-1) are as follows:
Structural units derived from ethylene: 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°C: 22
B value: 1.3

[Physical Properties of Ethylene-Based 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 molar amount was determined by intensity measurement using a ¹ H-NMR spectrometer. Details of the measurement conditions are described in WO 2015/122415.

<Mooney Viscosity>
The Mooney viscosity (ML(1+4) 100° C., 125° C.) was measured using a Mooney viscometer (Shimadzu Corporation, SMV202 type) in accordance with JIS K6300 (1994).

<B value>
Using o-dichlorobenzene-d ₄ /benzene-d ₆ (4/1 [v/v]) as the measurement solvent, ¹³ C-NMR spectrum (100 MHz, JEOL ECX400P) was measured at a measurement temperature of 120° C., and calculation was made based on the following formula (i).
B value=([EX]+2[Y])/[2×[E]×([X]+[Y])] (i)
[wherein [E], [X] and [Y] are each ethylene [A], a cyclic alkyl group having 4 to 20 carbon atoms,
and [EX] represents the molar fraction of structural units derived from an α-olefin [B] having 4 to 20 carbon atoms and a non-conjugated polyene [C].]

The ethylene-α-olefin-non-conjugated polyene copolymers used in the comparative examples of the present invention are shown below.

[Ethylene-α-olefin-non-conjugated 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 Trade name: Mitsui EPT 4045M: Mooney viscosity ML (1+4) 100°C = 45, ethylene content = 45 wt%, diene (ENB) content = 7.6 wt%.

[Trans polyoctenylene (M)]
As the trans-polyoctenylene (M), VESTENAMER 8012 (trade name) manufactured by Evonik Industries was used.

[Anti-aging agent (F)]
As the antioxidant (F),
Tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate] (trade name Irganox 1010, manufactured by BASF Japan) (F-1), and 2-mercaptobenzimidazole (trade name Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.) (F-2)
was used.

<Physical Properties of Ethylene-Based Copolymer Composition (Non-Crosslinked Product)>
<Measurement of Adhesion>
The adhesion between the layer [I] made of the uncrosslinked ethylene copolymer composition and the layer [II] containing a fiber material was measured by a probe tack test.
The test was carried out using a tack tester (TAC-II) manufactured by Rhesca. A stainless steel cylindrical probe with a diameter of 5 mm was brought into contact with the test specimen, and the tack (gf) generated when peeling was measured. The contact speed of the probe to the test specimen was 120 mm/min, the applied pressure was 50 gf, the applied pressure time was 20 seconds, the peel speed was 120 mm/min, and the temperature was 50°C.

<Physical Properties of Crosslinked Ethylene-Based Copolymer Composition>
<Tear strength>
A test piece measuring 150 mm x 50 mm was cut out from a crosslinked sheet having a thickness of 2 mm. Next, a slit having a length of 75 mm was made in the center of the test piece in the longitudinal direction, and the trouser tear strength was measured using a tensile tester (tensile speed: 200 mm/min, measurement environment temperature: 23°C). The tear strength was calculated by dividing the tear strength (N) by the sheet thickness (mm). The test was performed three times, and the average value was used.

<Durometer A hardness>
According to JIS K 6253, the hardness of the sheet (type A durometer, HA) was measured using six 2 mm crosslinked sheets having smooth surfaces, with the flat parts stacked to a thickness of about 12 mm. However, test pieces containing foreign matter, air bubbles, and scratches were not used. The dimensions of the measurement surface of the test piece were set so that the tip of the indenter could be measured at a position 12 mm or more away from the end of the test piece.

<Tensile stress at break, tensile elongation at break>
The tensile stress at break and the tensile elongation at break of the sheet were measured by the following method.
The sheet was punched out to prepare No. 3 dumbbell test pieces as described in JIS K 6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K6251, section 3, at a measurement temperature of 25°C and a tensile speed of 500 mm/min, and the tensile stress at break (TB) and tensile elongation at break (EB) were measured.

<Heat aging resistance>
A heat aging resistance test was carried out in accordance with JIS K 6257. That is, the sheet was aged in an oven at 180° C. for 70 hours, and then a tensile test was carried out under conditions of a measurement temperature of 23° C. and a tensile speed of 500 mm/min to measure the tensile elongation at break (EB).

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

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

Example 1
The ethylene copolymer (L-1) was masticated for 30 seconds, and 100 parts by mass of the masticated ethylene copolymer (L-1) was mixed with 5 parts by mass of zinc oxide (ZnO#1) as a crosslinking aid, 1 part by mass of stearic acid as a lubricant, 3 parts by mass of tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane [trade name Irganox 1010 manufactured by BASF Japan Ltd.] as an antiaging agent, 6 parts by mass of 2-mercaptobenzimidazole (trade name Sandant MB manufactured by Sanshin Chemical Industry Co., Ltd.), 50 parts by mass of carbon black [manufactured by Asahi Carbon Co., Ltd., trade name Asahi #70], 10 parts by mass of a softener [trade name Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.] manufactured by Evonik as trans polyoctenylene (M), and The mixture was mixed with 5 parts by mass of VESTENAMER 8012 (trade name: VESTENAMER Industries) in a 1.7 liter Banbury mixer (manufactured by Kobe Steel, Ltd.) for 2 minutes. The ram was then raised and cleaned, and the mixture was mixed for another minute and discharged at about 150° C. to obtain a compound. The mixing was performed at a filling rate of 70%.

Next, 177 parts by mass of this compound was wound around 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 3 parts by mass of melamine resin (N-1) and 6.8 parts by mass of dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., product name Mitsui DCP-40C) as a crosslinking agent were added and kneaded for 10 minutes, then separated into sheets to prepare uncrosslinked sheets with thicknesses of 2 mm and 3 mm.

The adhesive strength (gf) of the resulting uncrosslinked sheet having a thickness of 2 mm was measured by the method described above. The results are shown in Table 1.
Next, the obtained uncrosslinked sheet having a thickness of 2 mm 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 by the methods described above.
The results are shown in Table 1.

Example 2
An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained in the same manner as in Example 1, except that the types and amounts of the ingredients (additives) were changed to the ingredients and amounts shown in Table 1 instead of the composition used in Example 1, and the physical properties, etc. were evaluated by the methods described above.
The results are shown in Table 1.

Comparative Example 1
Except for using copolymer-2 instead of copolymer (L-1) used in Example 1, and changing the types and amounts of the blending agents (additives) to those shown in Table 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 methods described above.
The results are shown in Table 1.

Comparative Example 2
An uncrosslinked copolymer composition, a crosslinked copolymer composition, and a laminate were obtained in the same manner as in Example 1, except that the types and amounts of the ingredients (additives) were changed to the ingredients and amounts shown in Table 1 instead of the composition used in Example 1, and the physical properties, etc. were evaluated by the methods described above.
The results are shown in Table 1.

As is clear from Table 1, the copolymer composition of Example 1 containing 3 parts by mass of (F-1) and 6 parts by mass of (F-2) as the antioxidant (F), totaling 9 parts by mass, and the copolymer composition of Example 2 containing 4 parts by mass of (F-1) and 8 parts by mass of (F-2), totaling 13 parts by mass, had large tack (gf) [Peak Value @ 50°C] generated upon peeling, at 404.9 gf and 625.8 gf, respectively, and the peel strengths of the laminates were also strong, at 161.8 N/cm and 187.2 N/cm, respectively. On the other hand, the copolymer composition (Comparative Example 2) containing 2 parts by mass of (F-1) and 4 parts by mass of (F-2), totaling 6 parts by mass, as the antioxidant (F), which is smaller than those of Examples 1 and 2, had a low tack (gf) generated upon peeling, at 339 gf, and the peel strength of the laminate was also weak, at 32.5 N/cm.
That is, as can be seen from Table 1, the copolymer compositions of the Examples have better adhesion and are superior in interlayer adhesive strength of the laminate, as compared with the copolymer compositions of the Comparative Examples.

Claims (9)

An ethylene-based copolymer composition comprising the following ethylene/α-olefin/non-conjugated polyene copolymer (L), the following trans-polyoctenylene (M), and a specific amount of the following antioxidant (F).
(L) An ethylene/α-olefin/non-conjugated polyene copolymer containing a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], which satisfies the following requirements (1) to (4):
(M) trans polyoctenylene.
The antioxidant (F) is contained in an amount of 8 to 24 parts by mass per 100 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer (L).
(1) the molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] to the structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms is 40/60 to 90/10;
(2) the content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol %, based on 100 mol % of the total of the structural units [A], [B] and [C];
(3) Mooney viscosity ML(1+4)125°C at 125°C is 5 to 100,
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2[Y]) / (2 x [E] x ([X] + [Y])) (i)
[Here, [E], [X] and [Y] respectively represent the molar fractions of ethylene [A], the α-olefin [B] having 4 to 20 carbon atoms, and the non-conjugated polyene [C], and [EX] represents the dyad chain fraction of ethylene [A]-α-olefin [B] having 4 to 20 carbon atoms.] The ethylene-based copolymer composition according to claim 1, wherein the α-olefin [B] having 4 to 20 carbon atoms constituting the ethylene-α-olefin-non-conjugated polyene copolymer (L) is 1-butene. The ethylene-based copolymer composition according to claim 1, further comprising an organic peroxide as a crosslinking agent. The ethylene copolymer composition according to claim 1, which contains 0.5 to 50 parts by mass of trans-polyoctenylene (M) per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (L). A laminate comprising a layer [I] made of the ethylene copolymer composition according to any one of claims 1 to 4 and a layer [II] containing a fiber material in contact with each other. The laminate according to claim 5, in which the ethylene copolymer composition is crosslinked. The laminate of claim 5, wherein the fiber material of layer [II] includes RFL-treated fibers. The laminate according to claim 5, wherein the textile material of the layer [II] is canvas. An industrial belt comprising the laminate according to claim 5.