JP7458860B2 - Composition for power transmission belts and its uses power transmission belts - Google Patents

Description

The present invention relates to a composition for power transmission belts and its uses.

Transmission belts are used, for example, as friction transmission belts such as V-belts and V-ribbed belts such as wrapped belts and low-edge belts, as well as interlocking transmission belts such as timing belts, for automobiles, motorcycles, and general industrial machinery. Widely used.

Transmission belts are required to have adhesion, elasticity, and abrasion resistance. Chloroprene rubber is commonly used to manufacture power transmission belts that meet the above properties. Furthermore, in order to improve heat resistance and cold resistance, and to reduce weight, the use of ethylene/propylene/non-conjugated polyene copolymer rubber in place of chloroprene rubber is being considered (for example, see Patent Documents 1 and 2). ). Further, Patent Document 3 describes that a power transmission belt with improved wear resistance can be obtained from a rubber composition containing a specific ethylene/α-olefin/nonconjugated polyene copolymer.

On the other hand, Patent Document 4 describes that a specific ethylene/α-olefin having 4 to 20 carbon atoms/nonconjugated polyene copolymer has an excellent balance of adhesiveness, processability, and fluidity.

Japanese Patent Application Publication No. 2001-310951 JP2012-215212A Japanese Patent Application Publication No. 2016-44198 International Publication No. 2015/122415

According to the investigations of the present inventors, there is room for improvement in wrapped belts using conventional rubber compositions from the viewpoint of adhesion to diene rubber constituting the core material.
In order to solve the problems in the conventional techniques, an object of the present invention is to provide a composition for a power transmission belt which has excellent heat resistance and excellent adhesion to a core material.

The present inventors conducted extensive studies to solve the above-mentioned problems, and found that the above-mentioned problems could be solved by a composition for power transmission belts having the following structure, thereby completing the present invention. That is, the present invention relates to, for example, the following [1] to [4].

［２］
前記共重合体（Ｂ）が下記要件（ｂ－１）および（ｂ－２）を満たす前記［１］の伝動ベルト用組成物。
要件（ｂ－１）：エチレンに由来する構造単位〔ｂ１〕と炭素数３～２０のα－オレフィンに由来する構造単位〔ｂ２〕とのモル比（〔ｂ１〕／〔ｂ２〕）が、５０／５０～７５／２５である。
要件（ｂ－２）：下記式（ｉｂ）で表されるＢ値が１．０５以下である。
Ｂ値＝［ＥＰ］／（２［Ｅ］×［Ｐ］） …（ｉｂ）
〔式（ｉｂ）において、［Ｅ］および［Ｐ］は、それぞれエチレンに由来する構造単位〔ｂ１〕のモル分率および炭素数３～２０のα－オレフィンに由来する構造単位〔ｂ２〕のモル分率を表し、［ＥＰ］は、エチレン・炭素原子数３～２０のα－オレフィンのダイアッド連鎖分率を表す。〕
［３］
前記［１］または［２］の組成物あるいはその架橋物を含む層［Ｉ］と、前記層［Ｉ
］と接する、ジエン系ゴムまたはその架橋物を含む層［II］との積層体。
［４］
前記［３］の積層体を含む伝動ベルト。 [1]
(B) A structural unit [b1] derived from ethylene, a structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms, and a partial structure represented by the following general formula (I) or (II). A non-conjugated polyene containing a structural unit [b3] derived from a non-conjugated polyene containing only one in the molecule and a total of two or more partial structures represented by the following general formula (I) or (II) in the molecule. an ethylene/α-olefin/nonconjugated polyene copolymer containing the derived structural unit [b4],
(A) Ethylene α containing a structural unit [a1] derived from ethylene, a structural unit [a2] derived from an α-olefin having 4 to 20 carbon atoms, and a structural unit [a3] derived from a non-conjugated polyene. - Olefin/non-conjugated polyene copolymer (excluding the above copolymer (B)),
A composition for a power transmission belt containing (C1) a hindered phenol anti-aging agent and (C2) a sulfur anti-aging agent.

[2]
The composition for a power transmission belt according to [1] above, wherein the copolymer (B) satisfies the following requirements (b-1) and (b-2).
Requirement (b-1): The molar ratio ([b1]/[b2]) of the structural unit [b1] derived from ethylene and the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms is 50 /50 to 75/25.
Requirement (b-2): The B value expressed by the following formula (ib) is 1.05 or less.
B value = [EP] / (2 [E] × [P]) ... (ib)
[In formula (ib), [E] and [P] are the mole fraction of the structural unit [b1] derived from ethylene and the mole of the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms, respectively. [EP] represents the dyad chain fraction of ethylene/α-olefin having 3 to 20 carbon atoms. ]
[3]
A layer [I] containing the composition of [1] or [2] or a crosslinked product thereof;
] in contact with a layer [II] containing a diene rubber or a crosslinked product thereof.
[4]
A power transmission belt including the laminate of [3] above.

The power transmission belt composition of the present invention has excellent heat resistance and excellent adhesion to the core material.

The present invention will be explained in further detail.
[Composition for power transmission belt]
The composition for power transmission belts of the present invention (hereinafter also referred to as "composition of the present invention") comprises an ethylene/α-olefin/non-conjugated polyene copolymer (A) described below and an ethylene/α-olefin/non-conjugated polyene copolymer (A). Conjugated polyene copolymer (B), (C1) hindered phenol anti-aging agent,
(C2) A sulfur-based anti-aging agent.

The power transmission belt composition of the present invention contains an ethylene/α-olefin/non-conjugated polyene copolymer (A) and an ethylene/α-olefin/non-conjugated polyene copolymer (B) as rubber components.

<Ethylene/α-olefin/non-conjugated polyene copolymer (A)>
Ethylene/α-olefin/non-conjugated polyene copolymer (A) (hereinafter also simply referred to as "copolymer (A)") has a structural unit [a1] derived from ethylene [A1] and a carbon number A copolymer having a structural unit [a2] derived from 4 to 20 α-olefins [A2] and a structural unit [a3] derived from a non-conjugated polyene [A3] (however, the copolymer (B ).

The copolymer (A) has a structural unit [a1] derived from ethylene [A1], a structural unit [a2] derived from at least one type of α-olefin having 4 to 20 carbon atoms [A2], and at least one It can have a structural unit [a3] derived from a type of non-conjugated polyene [A3].

<<α-Olefin having 4 to 20 carbon atoms [A2]>>
Examples of the α-olefins [A2] having 4 to 20 carbon atoms include linear α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-nonadecene, and 1-eicosene; and side chain-containing α-olefins such as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among these, from the viewpoint of a well-balanced and excellent adhesion and mechanical strength, α-olefins having 4 to 10 carbon atoms are preferred, 1-butene, 1-hexene, and 1-octene are more preferred, and 1-butene is even more preferred.
The α-olefins [A2] having 4 to 20 carbon atoms can be used alone or in combination of two or more.

《Nonconjugated polyene [A3]》
Examples of the non-conjugated polyene [A3] include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6 - Chain nonconjugated dienes such as octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene- Cyclic non-conjugated dienes such as 2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 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, 4-ethylidene-8-methyl-1, Examples include trienes such as 7-nonadiene. Among these, from the viewpoint of vulcanization rate, linear nonconjugated dienes such as 1,4-hexadiene, and cyclic nonconjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred; Conjugated dienes are more preferred, and 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are even more preferred.
Non-conjugated polyene [A3] can be used alone or in combination of two or more.

Examples of the copolymer (A) include ethylene/1-butene/1,4-hexadiene copolymer, ethylene/1-pentene/1,4-hexadiene copolymer, and ethylene/1-hexene/1,4-hexadiene copolymer. -Hexadiene copolymer, ethylene/1-heptene/1,4-hexadiene copolymer, ethylene/1-octene/1,4-hexadiene copolymer, ethylene/1-nonene/1,4-hexadiene copolymer Coalescence, ethylene/1-decene/1,4-hexadiene copolymer, ethylene/1-butene/1-octene/1,4-hexadiene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene copolymer Polymer, 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, and ethylene/1-butene/1-octene/5-ethylidene-2-norbornene copolymer. Among these, ethylene/1-butene/5-ethylidene-2-norbornene copolymer is preferred from the viewpoint of mechanical strength.

<<Requirements (a-1) to (a-4')>>
The copolymer (A) preferably satisfies any one or more of the following requirements (a-1) to (a-3), more preferably satisfies the following requirements (a-1) to (a-3). In one embodiment, the copolymer (A) preferably satisfies the later-described requirement (a-4) or (a-4').

Requirement (a-1): The molar ratio ([a1]/[a2]) of the structural unit [a1] derived from ethylene and the structural unit [a2] derived from an α-olefin having 4 to 20 carbon atoms is It is 40/60 to 90/10.
The copolymer (A) 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 the molar ratio ([a1]/[a2]) is preferably 45/55, more preferably 50/50, particularly preferably 55/45. Further, the upper limit of the molar ratio ([a1]/[A2]) is preferably 80/20, more preferably 75/25, and even more preferably 70/30.

Requirement (a-2): The content ratio of the structural unit [a3] derived from the non-conjugated polyene is 100 mol%, with the total of the structural unit [a1], the structural unit [a2] and the structural unit [a3] being 100 mol%. , 0.1 to 6.0 mol%. The copolymer (A) having this content within the above range has sufficient crosslinkability and flexibility.
The lower limit of the content of the structural unit [a3] is preferably 0.5 mol%. The upper limit of the content of the structural unit [a3] is preferably 4.0 mol%, more preferably 3.5 mol%, and even more preferably 3.0 mol%.
The proportions of the structural unit [a1], the structural unit [a2] and the structural unit [a3] can be determined by intensity measurement using a ¹ H-NMR spectrometer.

Requirement (a-3): The B value expressed by the following formula (ia) is 1.20 or more.
B value = ([EB]+2[Y])/[2×[E]×([B]+[Y])]…(ia)
[In formula (ia), [E], [B] and [Y] are the mole fraction of the structural unit [A1] derived from ethylene, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms, respectively. The mole fraction of [A2] and the mole fraction of the structural unit [A3] derived from the nonconjugated polyene are shown, and [EB] shows the ethylene-α-olefin dyad chain fraction having 4 to 20 carbon atoms. ]
The B value is preferably 1.20 to 1.80, more preferably 1.22 to 1.40.
The copolymer (A) that satisfies requirement (a-3) has high alternation of monomer units constituting the copolymer and low crystallinity, so that the processability of the resulting composition is improved.
The B value is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer, and [E], [B], [Y], and [EB] in the above formula (ia) are ¹³ C- It can be determined by measuring an NMR spectrum and based on the reports of JCRandall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and others.

Requirement (a-4): Mooney viscosity ML(1+4) 100°C is 5 to 150.
The Mooney viscosity ML(1+4) 100°C is preferably 5 to 100, more preferably 5 to 50. The copolymer (A) having a Mooney viscosity within the above range has good processability and fluidity, exhibits good post-processing quality (ribbon handling properties), and has excellent rubber physical properties.

Requirement (a-4'): Mooney viscosity ML(1+4) 125°C is 3 to 100.
The Mooney viscosity ML(1+4)125°C is preferably 3 to 70, more preferably 3 to 30. The copolymer (A) having a Mooney viscosity in the above range has good processability and flowability, and also exhibits good post-treatment quality (ribbon handling property) and has excellent rubber physical properties.

The composition of the present invention may contain one type of copolymer (A), or may contain two or more types of copolymers (A).
The copolymer (A) generally has higher adhesiveness than the ethylene/propylene/non-conjugated polyene copolymer contained in conventional rubber compositions. The composition has strong bonds between the components and has excellent belt processability and moldability.

<<Method for producing copolymer (A)>>
Copolymer (A) can be obtained by 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 International Publication No. 2015/122415, particularly paragraphs [0249] to [0320] of the publication can be adopted.

<Ethylene/α-olefin/non-conjugated polyene copolymer (B)>
The ethylene/α-olefin/nonconjugated polyene copolymer (B) (hereinafter also simply referred to as "copolymer (B)") has a structural unit [b1] derived from ethylene and a carbon number of 3 to 20. Structural unit [b2] derived from α-olefin [B2] and non-conjugated polyene [B3] containing only one partial structure represented by the following general formula (I) or (II) in the molecule Contains a structural unit [b3] and a structural unit [b4] derived from a non-conjugated polyene [B4] containing a total of two or more partial structures represented by the following general formula (I) or (II) in the molecule. .

The copolymer (B) has a structural unit [b1] derived from ethylene [B1], a structural unit [b2] derived from at least one type of α-olefin having 4 to 20 carbon atoms [B2], and at least one It can have a structural unit [b3] derived from a type of non-conjugated polyene [B3] and a structural unit [b4] derived from at least one type of non-conjugated polyene [B4].

《α-olefin having 3 to 20 carbon atoms [B2]》
Examples of the α-olefin [B2] having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1- Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene, are preferred, and propylene is particularly preferred, since they have good mechanical strength. These α-olefins may be used alone or in combination of two or more.

<<Non-conjugated polyene [B3]>>
The non-conjugated polyene [B3] is
A non-conjugated polyene containing one partial structure represented by the general formula (I) in the molecule and no partial structure represented by the general formula (II) in the molecule, or a non-conjugated polyene containing one partial structure represented by the general formula (II) in the molecule and no partial structure represented by the general formula (I) in the molecule.

The partial structure represented by the above general formula (I) is a partial structure of a cyclic olefin. In other words, the partial structure represented by the above general formula (I) consists of two carbon atoms that are adjacent to each other and connected by a double bond that constitute the ring of the cyclic olefin, and one carbon atom for each of the two carbon atoms. It has a structure consisting of an atomic group containing two hydrogen atoms bonded to each other.

For example, 5-ethylidene-2-norbornene (ENB) corresponds to the non-conjugated polyene [B3] because it contains one partial structure represented by the above general formula (I) in one molecule. On the other hand, dicyclopentadiene (DCPD) contains two partial structures represented by the above general formula (I) in one molecule, and therefore falls under the non-conjugated polyene [B4] described below. 5-vinylidene-2-norbornene has one partial structure represented by the above general formula (I) in one molecule and one partial structure represented by the above general formula (II) in one molecule. Therefore, it corresponds to non-conjugated polyene [B4] described later.
Examples of the non-conjugated polyene [B3] include the following aliphatic polyenes and alicyclic polyenes.

Specific examples of the aliphatic polyene include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3- Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, Examples include 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, and among these, 7-methyl-1,6-octadiene is preferred. These aliphatic polyenes may be used alone or in combination of two or more.

The alicyclic polyene includes, for example, an alicyclic moiety having one carbon-carbon double bond (unsaturated bond) and a carbon atom bonded to the carbon atom constituting the alicyclic moiety through a carbon-carbon double bond. Specific examples include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, and 5-butylidene-2-norbornene (ENB). Examples include 2-norbornene, and 5-ethylidene-2-norbornene (ENB) is preferred.

Specific examples of other alicyclic polyenes include 2-methyl-2,5-norbornadiene and 2-ethyl-2,5-norbornadiene.

《Nonconjugated polyene [B4]》
The non-conjugated polyene [B4] is
A non-conjugated polyene containing two or more partial structures represented by the above general formula (I) in the molecule and not containing a partial structure represented by the above general formula (II) in the molecule,
A non-conjugated polyene containing two or more partial structures represented by the above general formula (II) in the molecule and no partial structure represented by the above general formula (I), or the above general formula (I) It is a non-conjugated polyene containing one or more partial structures represented by the above general formula (II) in its molecule.

The non-conjugated polyene [B4] is, for example, an alicyclic moiety having a carbon-carbon double bond (unsaturated bond) and a chain moiety bonded to a carbon atom constituting the alicyclic moiety, which has a vinyl group. Examples include alicyclic polyenes having a chain moiety and aliphatic polyenes having vinyl groups at both ends of the molecule. Specific examples include 5-alkenyl-2-norbornenes such as 5-vinyl-2-norbornene (VNB) and 5-allyl-2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, and tetracyclo[ 4,4,0,1 ^2.5 ,1 ^7.10 ]Alicyclic polyenes such as deca-3,8-diene; aliphatic polyenes such as α,ω-dienes such as 1,7-octadiene and 1,9-decadiene; Can be mentioned. These may be used alone or in combination of two or more.

Among these, 5-vinyl-2-norbornene (VNB), 5-alkenyl-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, 1,7-octadiene, and 1,9-decadiene are preferred, and 5-vinyl -2-norbornene (VNB) is particularly preferred.

<<Requirements (b-1) to (b-4)>>
The copolymer (B) preferably satisfies any one of the following requirements (b-1) to (b-4), and more preferably satisfies the following requirements (b-1) and (b-2).

Requirement (b-1): The molar ratio ([b1]/[b2]) of the structural unit [b1] derived from ethylene and the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms is 50 /50 to 75/25.
The molar ratio ([b1]/[b2]) is preferably 50/50 to 70/30, more preferably 55/45 to 65/35.

Requirement (b-2): The B value expressed by the following formula (ib) is 1.05 or less.
B value = [EP] / (2 [E] × [P]) ... (ib)
[In formula (ib), [E] and [P] are the mole fraction of the structural unit [b1] derived from ethylene and the mole of the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms, respectively. [EP] represents the dyad chain fraction of ethylene/α-olefin having 3 to 20 carbon atoms. ]

The B value is an index showing the randomness of the copolymerization monomer sequence distribution in the copolymer, and [E], [P], and [EP] in the above formula (ib) can be determined by measuring a ^13C -NMR spectrum based on the reports of JC Randal [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and others.
When the B value is 1.0, the randomness is highest, and the smaller the B value is, the higher the blockiness is, and conversely, the higher the B value is, the higher the alternation is.
It is preferable that the B value is within the above range in that the copolymer (B) has excellent blocking resistance.Furthermore, it is preferable that the B value is closer to 1.0 in that the copolymer (B) has excellent randomness and exhibits excellent low-temperature properties.

As the copolymer (B), an ethylene/propylene/ENB/VNB copolymer is particularly preferred.
Copolymer (B) can be produced by a conventionally known method, for example, the method described in [0057] to [0102] of JP 2014-208740A.

Requirement (b-3): The molar ratio ([B3]/[B4]) of the content of the structural unit [B3] derived from the non-conjugated polyene [B3] to the content of the structural unit [B4] derived from the non-conjugated polyene [B4] is 85/15 to 99.5/0.5.
The molar ratio ([B3]/[B4]) is preferably from 90/10 to 99.5/0.5, and more preferably from 95/5 to 99.5/0.5.

Requirement (b-4): The total content of structural units derived from non-conjugated polyene [B3] and structural units derived from non-conjugated polyene [B4] must be On the other hand, it is preferably 0.5 to 4.5 mol%, more preferably 1.0 to 4.5 mol%, and even more preferably 2.0 to 4.5 mol%. It is preferable that the content is within the above range from the viewpoint of rubbery properties (for example, permanent elongation and compression set) of the copolymer (B).

The respective proportions of structural unit [b1], structural unit [b2], structural unit [b3] and structural unit [b4] can be determined by intensity measurement using a ¹ H-NMR spectrometer.

The total content of copolymer (A) and copolymer (B) in the composition of the present invention is usually 20% by mass or more, preferably 30 to 90% by mass.
The mass ratio of copolymer (A) and copolymer (B) (copolymer (A)/copolymer (B)) is preferably 90/10 to 50/50, more preferably 80/20. ~60/40, more preferably 75/25 ~ 65/35.

<Hindered phenol anti-aging agent (C1)>
The composition for a power transmission belt according to the present invention contains a hindered phenol anti-aging agent (C1).
Specifically, the hindered phenol anti-aging agent (C1) is:
(1) 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenylbutane,
(2) 4,4'-butylidenebis-(3-methyl-6-t-butylphenol),
(3) 2,2-thiobis(4-methyl-6-t-butylphenol),
(4) 7-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate,
(5) Tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane,
(6) Pentaerythritol-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1010, manufactured by BASF),
(7) Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
(8) 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
(9) 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,
(10) Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate,
(11) 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
(12) N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy)-hydrocinnamide,
(13) 2,4-bis[(octylthio)methyl]-o-cresol,
(14) 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate-diethyl ester,
(15) Tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane,
(16) octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid ester,
(17) 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4-8,10- Examples include tetraoxaspiro[5,5]undecane. Among these, compound (6) is particularly preferred.

The content of the hindered phenol anti-aging agent (C1) in the composition of the present invention is preferably 0.2 to 5 parts by mass based on a total of 100 parts by mass of the copolymer (A) and the copolymer (B). Parts by weight, more preferably 0.5 to 4 parts by weight, still more preferably 1 to 3 parts by weight. When the content is within the above range, the effect of improving heat aging resistance is large and, moreover, crosslinking of the copolymer rubber (A) and the copolymer rubber (B) is not inhibited.

<Sulfur-based antioxidant (C2)>
Specific examples of the sulfur-based antioxidant (C2) include:
Imidazole-based antiaging agents such as 2-mercaptobenzimidazole (trade name: Sandant MB, manufactured by Sanshin Chemical Industry Co., Ltd.), zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, and zinc salt of 2-mercaptomethylimidazole;
Examples of the antiaging agents include aliphatic thioether-based antiaging agents such as dimyristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, and pentaerythritol-tetrakis-(β-lauryl-thiopropionate). Among these, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, and pentaerythritol-tetrakis-(β-lauryl-thiopropionate) are particularly preferred.

The content of the sulfur-based anti-aging agent (C2) in the composition of the present invention is 1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on a total of 100 parts by mass of the copolymer rubber (A) and the copolymer rubber (B). is 1 to 8 parts by weight, more preferably 1 to 6 parts by weight. When the content is within the above range, the effect of improving heat aging resistance is large and, moreover, crosslinking of the copolymer rubber (A) and the copolymer rubber (B) is not inhibited.

<Other ingredients>
The composition of the invention preferably further contains a crosslinking agent.
In addition to the above-mentioned components, the composition of the present invention may also include a softener, an inorganic filler (reinforcing agent), an anti-aging agent (however, a hindered phenolic anti-aging agent), to the extent that the effects of the present invention are not impaired. C1) and sulfur-based anti-aging agents (C2)), processing aids, activators, moisture absorbers, antistatic agents, colorants, lubricants, and thickeners. Furthermore, the composition of the present invention may further contain other polymers than the copolymer (A) and the copolymer (B), such as an elastomer and/or rubber, to the extent that the effects of the present invention are not impaired. Each of the components described below may be used alone or in combination of two or more.

《Crosslinking agent》
Examples of the crosslinking agent include crosslinking agents commonly used when crosslinking rubber, such as organic peroxides, sulfur compounds, phenolic resins, hydrosilicone compounds, amino resins, quinones or derivatives thereof, Examples include amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. Among these, organic peroxides and sulfur compounds are preferred.

Examples of organic peroxides include dicumyl peroxide, 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-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

When an organic peroxide is used as a crosslinking agent in the composition of the present invention, the content of the organic peroxide is usually 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 total of copolymer (A) and copolymer (B).

When using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking aid together. Examples of crosslinking aids include sulfur; quinonedioxime crosslinking aids such as p-quinonedioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl isocyanurate. Allyl crosslinking aids such as; maleimide crosslinking aids; divinylbenzene; magnesium oxide, zinc oxide type 2 (JIS K1410) (for example, "ZnO #1"; manufactured by Hakusui Tech Co., Ltd.), zinc white (for example, " Examples include metal oxides such as zinc oxide such as "META-Z 102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.).

When the composition of the present invention contains a crosslinking auxiliary agent, the content of the crosslinking auxiliary agent is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, per 1 mol of organic peroxide. More preferably, it is 1 to 5 mol.

When a sulfur compound is used as a crosslinking agent, specific examples include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

In the composition of the present invention, when a sulfur-based compound is used as a crosslinking agent, the content of the sulfur-based compound is usually 0 with respect to a total of 100 parts by mass of copolymer (A) and copolymer (B). .3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, more preferably 0.7 to 5.0 parts by weight.

When using a sulfur-based compound as a crosslinking agent, it is preferable to use a vulcanization accelerator together. Examples of vulcanization accelerators include:
N-Cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2-(4 -morpholinodithio)penzothiazole), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, dibenzothiazyl disulfide, etc. Sulfur accelerator;
Guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, diorthotolylguanidine;
Aldehyde amine-based vulcanization accelerators such as acetaldehyde/aniline condensates and butyraldehyde/aniline condensates;
Imidazoline vulcanization accelerators such as 2-mercaptoimidazoline;
Thiourea-based vulcanization accelerators such as diethylthiourea and dibutylthiourea;
Thiuram-based vulcanization accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide;
Dithioate salt-based vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, tellurium diethyldithiocarbamate;
Thiourea-based vulcanization accelerators such as ethylenethiourea (for example, Suncella 22C (trade name; manufactured by Sanshin Kagaku Kogyo Co., Ltd.)), N,N'-diethylthiourea, N,N'-dibutylthiourea;
Xanthate-based vulcanization accelerators such as zinc dibutylxatogenate;
Other examples include zinc white.

When the composition of the present invention contains a vulcanization accelerator, the content of the vulcanization accelerator is usually 0.05 parts per 100 parts by mass of the copolymer (A) and the copolymer (B). The amount is 1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight.

The vulcanization aid can be preferably used when the crosslinking agent is a sulfur-based compound, such as magnesium oxide, zinc oxide type 2 (JIS K1410) (for example, "ZnO #1"; manufactured by Hakusui Tech Co., Ltd.) , zinc oxide such as zinc white (for example, "META-Z 102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

When the composition of the present invention contains a vulcanization aid, the content of the vulcanization aid is usually 1 to 1 to 100 parts by mass in total of copolymer (A) and copolymer (B). It is 20 parts by mass.

《Softener》
Examples of softeners include:
Petroleum softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum;
Coal tar-based softeners such as coal tar;
Fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil;
Waxes such as beeswax and carnauba wax;
Fatty acids or salts thereof such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate;
naphthenic acid, pine oil, rosin or derivatives thereof;
Synthetic polymer substances such as terpene resin, petroleum resin, coumaron indene resin;
Ester softeners such as dioctyl phthalate and dioctyl adipate;
Others: microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon synthetic lubricating oil, tall oil, sub (factice)
Petroleum-based softeners are preferred, and process oils are more preferred.

When the composition of the present invention contains a softener, the content of the softener is usually 2 to 100 parts by mass, based on a total of 100 parts by mass of the copolymer (A) and the copolymer (B). Preferably it is 5 to 100 parts by mass.

《Inorganic filler (reinforcing material)》
Examples of inorganic fillers (reinforcing materials) include calcium carbonate (e.g., light calcium carbonate, heavy calcium carbonate, activated calcium carbonate), talc (e.g., finely divided talc), clay, silica, finely divided silicic acid, and carbon black. can be mentioned. Among these, carbon black is preferred.

When the composition of the present invention contains an inorganic filler, the content of the inorganic filler is usually from 0.1 to 100 parts by mass in total of copolymer (A) and copolymer (B). The amount is 200 parts by weight, preferably 10 to 200 parts by weight.

《Anti-aging agent (stabilizer)》
The composition of the present invention is an anti-aging agent (stabilizer) (excluding hindered phenol anti-aging agent (C1) and sulfur anti-aging agent (C2), hereinafter referred to as "other anti-aging agent"). ), it is possible to extend the life of a (crosslinked) molded article formed from the composition. Other anti-aging agents include, for example, amine-based anti-aging agents.

Examples of the amine antioxidant include aromatic secondary amine antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine.
When the composition of the present invention contains other anti-aging agents, the total content of the hindered phenolic anti-aging agent (C1), the sulfur-based anti-aging agent (C2) and the other anti-aging agents is The amount is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, based on a total of 100 parts by weight of the polymer (A) and the copolymer (B).

《Processing aid》
As the processing aid, a wide variety of processing aids that are generally blended into rubber can be used. Examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, and esters. Among these, stearic acid is preferred.

When the composition of the present invention contains a processing aid, the content of the processing aid is usually 10 parts by mass or less, preferably 8.0 parts by mass or less, per 100 parts by mass of the total of copolymer (A) and copolymer (B).

《Activator》
Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; diethylene glycol, polyethylene glycol, lecithin, triaryl utmerate, and zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids. Activators; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds.

When the composition of the present invention contains an active agent, the content of the active agent is usually 0.2 to 10 parts by weight based on a total of 100 parts by weight of copolymer (A) and copolymer (B). parts, preferably 0.3 to 5 parts by weight.

《Moisture absorbent》
Examples of the moisture absorbent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.

When the composition of the present invention contains a moisture absorbent, the content of the moisture absorbent is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass, per 100 parts by mass of the total of copolymer (A) and copolymer (B).

《Other polymers》
The composition of the present invention can further contain other polymers than the copolymer (A) and the copolymer (B).

Examples of other polymers that require crosslinking include rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, acrylic rubber, silicone rubber, fluororubber, and urethane rubber. It will be done.

Examples of other polymers that do not require crosslinking include block copolymers of styrene and butadiene (SBS), polystyrene-poly(ethylene-butylene)-polystyrene (SEBS), polystyrene-poly(ethylene-propylene)-polystyrene ( Styrene thermoplastic elastomer (TPS) such as SEPS), olefin thermoplastic elastomer (TPO), polyvinyl chloride elastomer (TPVC), ester thermoplastic elastomer (TPC), amide thermoplastic elastomer (TPA), urethane thermoplastic elastomer Examples include elastomers such as plastic elastomer (TPU) and other thermoplastic elastomers (TPZ).

When the composition of the present invention contains other polymers, the content of the other polymers is usually 100 parts by mass or less based on a total of 100 parts by mass of copolymer (A) and copolymer (B). , preferably 80 parts by mass or less.

<Preparation of composition>
The composition of the present invention contains a copolymer (A), a copolymer (B), a hindered phenol anti-aging agent (C1), and a sulfur anti-aging agent (C2), if necessary. It can be prepared by kneading the other components, for example, at a desired temperature using a kneader such as a mixer, kneader, or roll.

One embodiment of the composition of the invention is prepared, for example, as follows. The copolymer (A), the copolymer (B), the hindered phenol anti-aging agent (C1), the sulfur anti-aging agent (C2), and other components as necessary are mixed in a kneading machine. and kneaded to homogenize under predetermined heating conditions (for example, 80 to 200°C for 3 to 30 minutes) (Kneading A). In addition, in the A kneading, a crosslinking agent, etc., which crosslinks the copolymer (A) and the copolymer (B) when heated to the heating temperature of the A kneading, is not added.

After the temperature of the mixture kneaded in Kneading A is then lowered to below the crosslinking temperature of the crosslinking agent (for example, 130°C or lower), the crosslinking agent etc. that were not added in Kneading A are added to the mixture, and a predetermined amount is obtained. The composition of the present invention can be obtained by further kneading and homogenizing the mixture under heating conditions (for example, at a roll temperature of 30 to 80°C for 1 to 30 minutes) (kneading B).

The composition of the present invention has excellent heat resistance and excellent adhesion to the core material. The hindered phenol anti-aging agent (C1) and the sulfur-based anti-aging agent (C2) act as a radical generation source, and in the laminate of the present invention described later, the adhesion between the layer [I] and the layer [II] such as the core material. It is presumed that this contributes to improved sexual performance.

[Laminated body and power transmission belt]
The laminate of the present invention is a laminate of a layer [I] containing the composition of the present invention or a crosslinked product thereof, and a layer [II] containing a diene rubber or a crosslinked product thereof, which is in contact with the layer [I]. be.

The layer [I] can be formed from the composition of the present invention, and can be molded, for example, by a thermoforming method such as extrusion molding, injection molding, press molding, calendar molding, transfer molding, or foam molding. When crosslinking the composition, the crosslinking temperature is usually 140°C or higher, preferably 150 to 220°C, more preferably 160 to 200°C. Moreover, this crosslinking reaction can be performed in air.

The composition of the present invention has high adhesive strength suitable for molding processability and is excellent in belt processability. Further, by using the composition of the present invention, it is possible to produce a component for a power transmission belt that has high rubber elasticity, excellent abrasion resistance, heat resistance, and cold resistance.

The layer [I] can be suitably used as a component of a power transmission belt.
The layer [II] can be formed from diene rubber, and can be molded, for example, by a thermoforming method such as extrusion molding, injection molding, press molding, calendar molding, transfer molding, or foam molding.

Diene rubbers are rubbers having double bonds in the main chain of the polymer, examples of which include NR, IR, BR, SBR, NBR, CR and IIR. These may be used alone or in combination of two or more.

When the layer [II] is a crosslinked body of diene rubber, a crosslinking agent conventionally used for diene rubber can be used as the crosslinking agent for diene rubber. When crosslinking the diene rubber, the crosslinking temperature is usually 140°C or higher, preferably 150 to 220°C, more preferably 160 to 200°C. Moreover, this crosslinking reaction can be performed in air.

Further, the laminate of the present invention preferably includes a layer [I] containing the composition of the present invention containing the crosslinking agent (i.e., an uncrosslinked composition), and a layer [I] containing the diene rubber (i.e., an uncrosslinked rubber). This is a laminate obtained by heat-treating the layer [II] containing the above-mentioned polyester resin and the layer [II] in contact with each other at a crosslinking temperature.

In such a laminate, crosslinking occurs between the rubber components (the copolymer (A) and the copolymer (B)) contained in the composition of the present invention and the diene rubber. Therefore, it is considered that the layer [I] exhibits particularly excellent adhesion to the layer [II].

This crosslinking temperature is usually 140°C or higher, preferably 150 to 220°C, more preferably 160 to 200°C. Moreover, this heat treatment can be performed in air.
The power transmission belt of the present invention has the above-described laminate of the present invention.

Examples of the power transmission belt of the present invention include friction power transmission belts such as V belts and V-ribbed belts; interlocking power transmission belts such as timing belts. The transmission belt is, for example, a transmission belt for automobiles, a transmission belt for motorcycles, or a transmission belt for general industrial machinery. Examples of the V-belt include a wrapped belt and a raw-edge belt.

One embodiment of the power transmission belt has, for example, an adhesive rubber part in which a core wire is embedded, and can further include a bottom rubber part formed on the lower surface of the adhesive rubber part. The transmission belt may have an upper canvas formed on the adhesive rubber part and/or a lower canvas formed under the bottom rubber, as necessary. A canvas adhesive rubber layer may be interposed between the adhesive rubber part and the upper canvas and between the bottom rubber part and the lower canvas.

The composition of the present invention is suitably used, for example, to form a canvas adhesive rubber layer. Specifically, a crosslinked molded article formed from the composition of the present invention is suitably used as the canvas adhesive rubber layer.

The rubber used for forming the adhesive rubber part and/or the bottom rubber part is preferably the diene rubber mentioned above.
The core wire, which is a tensile member of the power transmission belt, extends in the longitudinal direction of the belt at the adhesive rubber portion. Examples of the core wire include polyester cords. The adhesive rubber portion surrounds the core wire and is bonded to the core wire.

In another embodiment, for example, the composition of the present invention may be placed around the core wire and crosslinked to form an adhesive rubber portion adhered to the core wire.
Examples of the canvas include those made of cotton, a blend of cotton and polyester, and those made of a blend of cotton and polyamide.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
[Measurement method - Physical properties of ethylene/α-olefin/non-conjugated polyene copolymer (A), etc.]
The physical properties of the ethylene/α-olefin/nonconjugated polyene copolymer (A) were measured as follows.

<Molar amount of structural units derived from ethylene, structural units derived from α-olefin, and structural units derived from non-conjugated polyene>
The molar amount was determined by intensity measurement using a ¹ H-NMR spectrometer. Details of the measurement conditions are described in International Publication No. 2015/122415.

<B value>
Using o-dichlorobenzene-d ₄ /benzene-d ₆ (4/1 [v/v]) as the measurement solvent, ^{the 13} C-NMR spectrum (100 MHz, JEOL ECX400P) was measured at a measurement temperature of 120°C. , Copolymer (A) was calculated based on the following formula (ia), and copolymer (B) was calculated based on the following formula (ib).
B value = ([EB]+2[Y])/[2×[E]×([B]+[Y])]…(ia)
B value=[EP]/(2[E]×[P])…(ib)
[The meanings of [E], [B], [P], [Y], [EB] and [EP] are as described above. ]

[Measurement method: Physical properties of composition, etc.]
The physical properties of the compositions and the like in the examples and comparative examples were measured as follows.
<Hardness test (Durometer-A)>
The flat portions of the 2 mm thick crosslinked sheets produced in the Examples and the like were overlapped to form a 12 mm thick sheet, and the hardness (JIS-A) was measured in accordance with JIS K6253.

<Tensile test: modulus, tensile stress at break, tensile elongation at break>
A No. 3 dumbbell test piece as described in JIS K6251 (1993) was prepared by punching out the crosslinked sheet with a thickness of 2 mm prepared in Examples, etc., and using this test piece, the test piece was tested as specified in JIS K6251, Section 3. A tensile test was conducted at a measurement temperature of 25°C and a tensile speed of 500 mm/min according to the method described above, and the tensile stress (25% modulus (M25) to 300% modulus (M300 )), tensile stress at break (TB) and tensile elongation at break (EB) were measured.

<Heat resistance test (heat aging resistance test)>
The crosslinked sheets having a thickness of 2 mm prepared in the examples and the like were subjected to a heat aging test in which the sheets were held at 140° C. for 72 hours in accordance with JIS K6257. The hardness, TB and EB of the sheets after the heat aging test were measured in the same manner as in the hardness test and tensile test.

AH (hardness after heat aging test - hardness before heat aging test), AR(TB) (TB after heat aging test / TB before heat aging test x 100), and AR(EB) (EB after heat aging test / EB before heat aging test x 100) were calculated.

<Peel test>
In accordance with JIS K6854-3, a T-peel test was carried out at a measurement temperature of 23.0° C., a test speed of 200 mm/min, and a test piece width of 25.0 mm, to measure the peel strength (the force required to peel off the vulcanization-bonded adherends).

[Manufacture example 1]
<Production of ethylene/α-olefin/non-conjugated polyene copolymer (A)>
According to the description in [Synthesis Example C1] of International Publication No. 2015/122415, an ethylene/1-butene/5-ethylidene-2-norbornene (ENB) copolymer (copolymer (A)) having the following physical properties was prepared. ) was obtained. Hereinafter, this will be referred to as "EBDM-1".
The structure and physical properties of EBDM-1 are as follows.
Structural unit derived from ethylene: 67.7 mol%
Structural unit derived from 1-butene: 30.0 mol%
Structural unit derived from ENB: 2.3 mol%
Mooney viscosity ML(1+4)100℃: 30
Mooney viscosity ML(1+4)125℃:22
B value: 1.3

[Manufacture example 2]
<Manufacture of adherend (layer (II))>
Details of the raw materials used to produce the adherends are shown in Table 1 below.

As a first step, 60 parts by mass of NR and 40 parts by mass of SBR were masticated for 1 minute using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.), and then 5 parts by mass of ZnO #1 was added to this. 1 part by mass of stearic acid, 70 parts by mass of carbon black (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.), and 3 parts by mass of Nocrac 224 were added and kneaded at 110° C. for 3 minutes. Thereafter, the ram was raised and cleaned, and kneaded for 2 minutes and discharged at 125°C to obtain the first stage formulation a. The kneading conditions at the time of preparing Compound a were a rotor rotation speed of 40 rpm and a floating weight pressure of 3 kgf/cm ² .

Next, after confirming that the temperature of Compound 1 had reached 40°C, using an 8-inch roll, 3.5 parts by mass of sulfur and a vulcanization accelerator (Suncellar CM, Sanshin Chemical Industry Co., Ltd.) were added to Compound A. Co., Ltd.) and 0.2 parts by mass of a vulcanization accelerator (Suncella DM, manufactured by Sanshin Kagaku Kogyo Co., Ltd.) were added and kneaded, and the mixture was separated after a kneading time of 8 minutes. , formulation b was obtained. The kneading conditions during the preparation of compound b were as follows: roll temperature: front roll/rear roll = 50°C/50°C; roll circumferential speed: front roll/rear roll = 18 rpm/15 rpm; roll gap: 3 mm.

Subsequently, the mixture b was subjected to a press treatment at 80° C. for 2 minutes using a press molding machine to produce an adherend (layer [II]) having a thickness of 1 mm.

[Example 1]
<Composition>
As a first step, using a BB-4 Banbury mixer (manufactured by Kobe Steel, Ltd.), 70 parts by mass of EBDM-1 obtained in Production Example 1 and 30 parts by mass of Mitsui EPT 9090M (manufactured by Mitsui Chemicals, Ltd.) were added. 5 parts by mass of zinc white (META-Z 102, manufactured by Inoue Lime Industry Co., Ltd.), 1 part by mass of stearic acid, and a hindered phenol antioxidant (Irganox 1010, manufactured by BASF). ) 2 parts by mass, sulfur-based anti-aging agent (Sandant MB, manufactured by Sanshin Kagaku Kogyo Co., Ltd.) 4 parts by mass, carbon black (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.) 120 parts by mass, silica (Nipsil VN3, 10 parts by mass of Tosoh Silica Co., Ltd.) and 80 parts by mass of paraffinic process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.) were added and kneaded at 120° C. for 2 minutes. Thereafter, the ram was raised and cleaned, and kneading was further performed for 2 minutes, and the mixture was discharged at 144° C. to obtain a first-stage formulation 1.

The kneading conditions for preparing Blend 1 were a rotor rotation speed of 40 rpm and a floating weight pressure of 3 kgf/cm ² .
Next, after confirming that the temperature of Formulation 1 reached 40°C, using an 8-inch roll, 1.2 parts by mass of sulfur and a vulcanization accelerator (Sunseller DM, Sanshin Kagaku Kogyo) were added to Formulation 1. Co., Ltd.) and 4 parts by weight of a vulcanization accelerator (RHENOCURE TP/S, Lanxess) were added and kneaded, and the mixture was separated for 8 minutes to obtain a blend 2.

The kneading conditions for preparing Compound 2 were as follows: roll temperature: front roll/back roll = 50°C/50°C; roll circumferential speed: front roll/back roll = 18 rpm/15 rpm; roll gap: 3 mm.

Compound 2 was press-treated at 80° C. for 2 minutes using a press molding machine to produce an unvulcanized sheet with a thickness of 1 mm. Further, Compound 2 was subjected to press treatment at 165° C. for 25 minutes using a press molding machine to produce a crosslinked sheet with a thickness of 2 mm.
Various measurements were performed on the obtained unvulcanized sheet and crosslinked sheet. The results are shown in Table 2.

<Laminated body>
The obtained unvulcanized sheet with a thickness of 1 mm was laminated on the adherend produced in Production Example 2, and press-treated at 160° C. for 10 minutes using a press molding machine to produce a laminate with a thickness of 2 mm.
A peel test was conducted on the obtained laminate. The results are shown in Table 2.

[Comparative Examples 1 and 2]
The same procedure as in Example 1 was conducted except that the composition and curing system were based on those listed in Table 2.
Materials used in Examples and Comparative Examples are shown in Table 2 below.

Claims (4)

(B) A structural unit [b1] derived from ethylene, a structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms, and a partial structure represented by the following general formula (I) or (II). A non-conjugated polyene containing a structural unit [b3] derived from a non-conjugated polyene containing only one in the molecule and a total of two or more partial structures represented by the following general formula (I) or (II) in the molecule. an ethylene/α-olefin/nonconjugated polyene copolymer containing the derived structural unit [b4],
(A) Ethylene α containing a structural unit [a1] derived from ethylene, a structural unit [a2] derived from an α-olefin having 4 to 20 carbon atoms, and a structural unit [a3] derived from a non-conjugated polyene. - For power transmission belts containing an olefin/non-conjugated polyene copolymer (excluding the copolymer (B) above), (C1) a hindered phenol anti-aging agent, and (C2) a sulfur anti-aging agent Composition.

The composition for a power transmission belt according to claim 1, wherein the copolymer (B) satisfies the following requirements (b-1) and (b-2).
Requirement (b-1): The molar ratio ([b1]/[b2]) of the structural unit [b1] derived from ethylene and the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms is 50 /50 to 75/25.
Requirement (b-2): The B value expressed by the following formula (ib) is 1.05 or less.
B value = [EP] / (2 [E] × [P]) ... (ib)
[In formula (ib), [E] and [P] are the mole fraction of the structural unit [b1] derived from ethylene and the mole of the structural unit [b2] derived from an α-olefin having 3 to 20 carbon atoms, respectively. [EP] represents the dyad chain fraction of ethylene/α-olefin having 3 to 20 carbon atoms. ] A layer [I] containing the composition according to claim 1 or 2 or a crosslinked product thereof, and the layer [I]
] in contact with a layer [II] containing a diene rubber or a crosslinked product thereof. A power transmission belt comprising the laminate according to claim 3.