JP2021074908A - Laminate - Google Patents

Abstract

To provide a laminate which has a layer formed from a composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer and a fiber base material layer and has an excellent adhesiveness to these layers.SOLUTION: There is provided a laminate which has a layer (X) formed from a composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) which has a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin (a2) and a structural unit derived from a non-conjugated polyene (a3), a peroxide-based crosslinking agent (B) and a crosslinking assistant (C) having two or more ethylenic double bonds and a fiber base material layer (Y), wherein the layer (X) and the fiber base material layer (Y) are brought into contact with each other.SELECTED DRAWING: None

Description

The present invention relates to a laminate.

Belts such as transmission belts and transport belts are widely used for automobiles, motorcycles and general industrial machinery. It has been studied to use an ethylene / propylene / non-conjugated polyene copolymer for producing a transmission belt (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2001-310951 Japanese Unexamined Patent Publication No. 2012-215212

In order to improve the mechanical strength of the belt, the present inventors stack a layer formed from a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and a fiber base material layer. It was investigated. However, according to the study by the present inventors, the layer formed from the composition containing ethylene, α-olefin, and non-conjugated polyene copolymer does not have sufficient adhesiveness to the fiber base material layer. It turned out that there was.

An object according to one aspect of the present invention is to have a layer formed from a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and a fiber base material layer, and to improve the adhesiveness of these layers. The purpose is to provide an excellent laminate.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by a laminate having the following configuration, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [9].

[1] Ethylene / α-olefin / non-conjugated polyene having a structural unit derived from ethylene (a1), a structural unit derived from α-olefin (a2), and a structural unit derived from non-conjugated polyene (a3). A layer (X) formed from a composition containing a copolymer (A), a peroxide-based cross-linking agent (B), and a cross-linking aid (C) having two or more ethylenic double bonds. And a fiber base material layer (Y), and the layer (X) and the fiber base material layer (Y) are in contact with each other.
[2] The laminate according to the above [1], wherein the non-conjugated polyene (a3) contains at least one selected from 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB). ..
[3] The laminate according to the above [1] or [2], wherein the α-olefin (a2) is propylene.
[4] The laminate according to any one of the above [1] to [3], wherein the fiber base material layer (Y) is a fiber base material containing fibers made of polyamide.
[5] A belt having the laminate according to any one of the above [1] to [4].
[6] The belt according to the above [5], which is a transmission belt or a transport belt.
[7] The belt according to the above [6], wherein the transmission belt is a V-belt, a flat belt, a round belt, a toothed belt or a V-ribbed belt.
[8] The transport belt according to the above [6], wherein the transport belt is a light transport belt, a cylindrical belt, a rough top belt, a flanged transport belt, a U-shaped guided transport belt, or a V-guided transport belt. Belt.
[9] An escalator handrail having the laminate according to any one of the above [1] to [4].

According to the present invention, a laminate having a layer formed from a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and a fiber base material layer and having excellent adhesiveness between these layers can be obtained. Can be provided.

The present invention will be described in detail.
One embodiment of the laminate of the present invention (hereinafter, also referred to as “laminate of the present embodiment”) includes ethylene / α-olefin / non-conjugated polyene copolymer (A), peroxide-based cross-linking agent (B), and the like. It also has a layer (X) formed from a composition containing a cross-linking aid (C) having two or more ethylenic double bonds, and a fiber substrate layer (Y). Here, the layer (X) and the layer (Y) are in contact with each other at least in a part.

[Fiber base layer (Y)]
Examples of the fibers constituting the fiber base material layer (Y) include fibers made of polyamide (hereinafter, also referred to as "polyamide fibers"), glass fibers, PAN-based carbon fibers, pitch-based carbon fibers, alumina fibers, and silicon carbide fibers. Examples include aluminum borate fiber and polyester fiber. Among these, polyamide fibers are preferable from the viewpoint of abrasion resistance and improvement of modulus.

The polyamide includes, for example, an aliphatic polyamide such as nylon 6, nylon 6, 6, nylon 6, 10; polymethaxylylene adipamide (MXD6), polyhexamethylene terephthalamide (6T), or a unit thereof. Semi-aromatic polyamides such as copolymerized polyamides; total aromatic polyamides such as polybenzamide, polyp-phenylene terephthalamide, and polym-phenylene isophthalamide can be mentioned.

The fibers are used as fiber substrates in the form of filaments or staple fibers and may be used in their own known forms such as cord yarns, spun yarns and the like. As the fiber base material layer (Y), a woven fabric, a knitted fabric, or a non-woven fabric is preferable, and a woven fabric is more preferable. These base materials may be used in a single layer or in multiple layers of two or more layers.

In one embodiment, the fiber base material layer (Y) may be a layer composed of polyamide fibers alone, or the polyamide fibers and other reinforcing fibers, such as glass fibers, PAN-based carbon fibers, pitch-based carbon fibers, alumina fibers, and silicon carbide. It may be a layer made of a combination of fibers, aluminum borate fibers, polyester fibers and the like.

The fiber diameter of the fibers constituting the fiber base material layer (Y) is not particularly limited, but is preferably 0.5 to 400 μm, more preferably 0.5 to 100 μm. The thickness of the fiber base material layer (Y) is preferably 10 to 5000 μm, more preferably 50 to 3000 μm.

[Layer (X)]
The layer (X) is a crosslink having two or more ethylenic double bonds with the ethylene / α-olefin / non-conjugated polyene copolymer (A) described below and the peroxide-based crosslinker (B). It is a layer formed from a composition containing an auxiliary agent (C) (hereinafter, also referred to as “the composition of the present embodiment”), and is preferably a layer formed by cross-linking the composition.

The present inventors have studied laminating a fiber base material layer on a rubber material used for a belt in order to increase the mechanical strength of a belt such as a transmission belt or a transport belt. Here, the adhesiveness between the rubber material and the synthetic fiber such as polyamide fiber is important, but the conventional ethylene / α-olefin / non-conjugated polyene copolymer rubber is compared with the polar rubber such as nitrile rubber and chloroprene rubber. Therefore, the adhesiveness with synthetic fibers tends to be inferior. On the other hand, the layer formed from the composition of the present embodiment has excellent adhesiveness to the fiber base material layer. Therefore, the laminate of the present embodiment can be suitably used, for example, as a constituent member of a belt.

<Ethylene / α-olefin / non-conjugated polyene copolymer (A)>
The ethylene / α-olefin / non-conjugated polyene copolymer (A) (hereinafter, also referred to as “copolymer (A)”) is derived from a structural unit derived from ethylene (a1) and from α-olefin (a2). It has a structural unit and a structural unit derived from a non-conjugated polyene (a3).

Examples of the α-olefin (a2) include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1 Examples thereof include α-olefins having 3 to 20 carbon atoms such as −tetradecene, 1-hexadecene, and 1-eikosen. Of these, α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene and 1-butene are more preferable. Such α-olefins are preferable because the raw material cost is relatively low, the obtained copolymer (A) exhibits excellent mechanical properties, and a molded product having rubber elasticity can be obtained.

One kind or two or more kinds of α-olefins (a2) can be used. That is, the copolymer (A) contains a structural unit derived from at least one α-olefin (a2), and even if it contains a structural unit derived from two or more types of α-olefin (a2). Good.

In the copolymer (A), the molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) and the structural unit derived from α-olefin (a2) is preferably 50/50. It is in the range of ~ 85/15, more preferably 53/47 to 83/17, and even more preferably 55/45 to 80/20. By using such a copolymer (A), a transmission belt having excellent heat resistance, cold resistance and abrasion resistance can be obtained. The content of the structural unit derived from ethylene (a1) and the content of the structural unit derived from α-olefin (a2) in the copolymer (A) can be determined by ^{13 C-NMR.}

Examples of the non-conjugated polyene (a3) include a cyclic non-conjugated polyene and a chain-shaped non-conjugated polyene. Cyclic non-conjugated polyenes include, for example, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB), norbornadiene, and methyltetrahydroindene. Examples of the chain-like non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadien, 8-methyl-4-ethylidene-1,7-nonadien, and 4-ethylidene-1,7-undecadien. Can be mentioned. Among these, the non-conjugated polyene (a3) is ENB and VNB because it is highly available, has good reactivity with peroxide during the cross-linking reaction after polymerization, and easily improves the heat resistance of the composition. It is preferable to contain at least one selected from, and it is more preferable that the non-conjugated polyene (a3) is at least one selected from ENB and VNB.

One kind or two or more kinds of non-conjugated polyenes (a3) can be used.
The mass fraction of the structural unit derived from the non-conjugated polyene (a3) is in 100% by mass of the copolymer (A) (that is, in 100% by mass of the total mass fraction of all structural units), preferably 0.01 to. It is 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. Such a copolymer (A) has sufficient hardness and excellent mechanical properties, and when crosslinked using a peroxide, it exhibits a high crosslinking rate. The content of the structural unit derived from the non-conjugated polyene (a3) in the copolymer (A) can be determined by ^{13 C-NMR.}

¹³ C-NMR measurement conditions are, for example, using an ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), measurement temperature: 120 ° C., measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, number of integrations. : 8000 times.

The iodine value of the copolymer (A) is preferably 1 to 40 g / 100 g, more preferably 2 to 35 g / 100 g, and further preferably 3 to 30 g / 100 g. The iodine value can be determined by the titration method. For example, the following method. 0.5 g of the copolymer (A) is dissolved in 60 ml of carbon tetrachloride, a small amount of whistle reagent and a 20% potassium iodide solution are added, and the mixture is adjusted with a 0.1 mol / L sodium thiosulfate solution. A starch indicator is added near the end point, and the mixture is adjusted until the lilac disappears while stirring well, and the g number of iodine is calculated as the amount of halogen consumed per 100 g of the sample.

Specific examples of the copolymer (A) include ethylene / propylene / non-conjugated polyene copolymer and ethylene / 1-butene / non-conjugated polyene copolymer.
The copolymer (A) has an intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C., preferably 0.8 to 5.0 dl / g, more preferably 1.0 to 4.5 dl / g. More preferably, it is in the range of 1.5 to 4.0 dl / g.

_{The copolymer (A) has a Mooney viscosity ML (1 + 4)} (100 ° C.) at 100 ° C., which is obtained by measuring according to ASTM D 1646, preferably 1 to 200, more preferably 10 to 100 ° C. In range.

The copolymer (A) can be produced, for example, by a conventionally known method using a polymerization catalyst such as a vanadium-based catalyst or a metallocene-based catalyst.
The composition of the present embodiment may contain one kind of copolymer (A) or may contain two or more kinds of copolymers (A). The content of the copolymer (A) in the composition of the present embodiment is usually 20% by mass or more, preferably 25 to 90% by mass.

<Peroxide cross-linking agent (B)>
The composition of the present embodiment contains a peroxide-based cross-linking agent (B). It is considered that the copolymer (A) can be satisfactorily crosslinked by using the peroxide-based cross-linking agent (B), and the heat-resistant aging property of the obtained layer (X) can be enhanced.

As the peroxide-based cross-linking agent (B), an organic peroxide is preferable. Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di-(. tert-Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexin-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1- Bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) ballerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4 -Dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide can be mentioned.

The composition of the present embodiment may contain one kind of peroxide-based cross-linking agent (B), or may contain two or more kinds of peroxide-based cross-linking agents (B).
In the composition of the present embodiment, the content of the peroxide-based cross-linking agent (B) is 100 in total of the copolymer (A) and other polymers (rubber, etc.) that need to be cross-linked, which are blended as necessary. It is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and further preferably 0.5 to 10 parts by mass with respect to parts by mass. In such an embodiment, cross-linking proceeds satisfactorily, and the obtained layer (X) is preferable from the viewpoint of heat resistance and abrasion resistance.

<Crosslinking aid (C) having two or more ethylenic double bonds>
The composition of this embodiment contains a cross-linking aid (C) having two or more ethylenic double bonds. By using the cross-linking aid (C) together with each of the above components, the adhesiveness between the layer (X) and the fiber base material layer (Y) can be improved, and further, the mechanical strength and cold resistance of the obtained laminate can be improved. It tends to improve resistance and wear resistance.

The number of ethylenic double bonds in the cross-linking aid (C) is preferably 2 to 6, more preferably 2 to 4. It is considered that by using the cross-linking aid (C), for example, a good network can be formed between the copolymers (A).

Examples of the cross-linking aid (C) include (meth) acrylic cross-linking aids such as ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; allyl-based cross-linking such as diallyl phthalate and triallyl isocyanurate. Auxiliary agent: Vinyl-based cross-linking auxiliary agent such as divinylbenzene can be mentioned. Among these, a (meth) acrylic cross-linking aid is preferable, and ethylene glycol dimethacrylate is more preferable.

The composition of the present embodiment may contain one kind of cross-linking aid (C) or may contain two or more kinds of cross-linking aid (C).
In the composition of the present embodiment, the content of the cross-linking aid (C) is preferably 0.01 to 22 mol, more preferably 0.1 to 1 mol, based on 1 mol of the peroxide-based cross-linking agent (B). It is 11 mol, more preferably 0.1 to 8 mol. In such an embodiment, cross-linking proceeds satisfactorily, and the obtained layer (X) is preferable from the viewpoint of heat resistance and abrasion resistance.

<Carbon black (D)>
The composition of the present embodiment may further contain carbon black (D). Carbon black (D) is, for example, a component that contributes to improving the mechanical strength, modulus, and wear resistance of the obtained layer (X).

Examples of carbon black (D) include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. The surface of the carbon black may be treated with a silane coupling agent. Commercially available carbon blacks include, for example, "Asahi # 55G", "Asahi # 50HG", "Asahi # 60G", "Asahi # 60UG", "Asahi # 70" (trade name, manufactured by Asahi Carbon Co., Ltd.). Examples include "Seast V" and "Seast SO" (trade name, manufactured by Tokai Carbon Co., Ltd.).

The composition of the present embodiment may contain one type of carbon black (D) or may contain two or more types of carbon black (D).
When the composition of the present embodiment contains carbon black (D), the content of carbon black (D) is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the copolymer (A). Yes, more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass. Such an embodiment is preferable from the viewpoint of the mechanical strength of the obtained layer (X) and the processability of the composition of the present embodiment.

<Short fiber (E)>
The composition of the present embodiment may further contain short fibers (E). By using the short fibers (E), the modulus and mechanical strength of the layer (X) formed from the above composition can be improved. Since the copolymer (A) is also excellent in kneadability with the short fibers (E), the composition of the present embodiment tends to be excellent in molding processability even if it contains the short fibers (E). ..

The short fiber (E) is made of, for example, a synthetic resin such as polyamide, polyimide, polyester, polyvinyl alcohol, rayon, polyolefin, polyarylate, polyphenylene sulfide, polyether ether ketone, polyparaphenylene benzobisoxazole, and a fluoropolymer. Fiber: Natural fibers such as cotton and wood cellulose fibers can be mentioned. Among these, short fibers made of synthetic resin are preferable, and short fibers made of polyamide are more preferable. The short fibers (E) are usually not short fibers formed from the copolymer (A).

Examples of the polyamide include polycapramid, poly-ω-aminoheptanoic acid, poly-ω-aminononanoic acid, polyundecaneamide, polyethylenediamine adipamide, polytetramethylene adipamide, polyhexamethylene adipamide, and polyhexamethylene. Aliper polyamides such as sebacamide, polyhexamethylene dodecamide, polyoctamethylene adipamide, polydecamethylene adipamide; polyparaphenylene terephthalamide (trade name "Kevlar", manufactured by Toray DuPont), poly Metaphenylene isophthalamide, copolyparaphenylene-3,4'-oxydiphenylene terephthalamide, polymethoxyylene adipamide, polymethoxylylene pimmelamide, polymethoxylylene aramid, polyparaxylene aramid, poly Aromatic polyamide (aramid) such as paraxylylene decanamide can be mentioned.

As the short fibers (E), short fibers made of aromatic polyamide, that is, aramid short fibers are preferable, and polyparaphenylene terephthalamide is preferable from the viewpoint of further improving the tensile stress and tear strength of the obtained layer (X). Short fibers, polymetaphenylene isophthalamide short fibers, and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide short fibers are more preferable.

The average fiber length of the short fibers (E) is usually 0.1 to 50 mm, preferably 0.5 to 10 mm, and more preferably 0.5 to 6 mm. The fiber diameter of the short fiber (E) is usually 0.1 to 100 μm, preferably 0.1 to 25 μm, and more preferably 1 to 20 μm.

The average fiber length of the short fibers (E) is determined by, for example, taking a photograph of the short fibers with an optical microscope, measuring the lengths of 100 randomly selected short fibers in the obtained photographs, and calculating the arithmetic mean. It can be obtained by doing.

The short fiber (E) may be a chopped fiber (cut fiber) -like short fiber or a pulp-like short fiber having fibrils.
The composition of the present embodiment may contain one kind of short fibers (E) or two or more kinds of short fibers (E).

When the composition of the present embodiment contains short fibers (E), the content of the short fibers (E) is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the copolymer (A). It is more preferably 0.1 to 30 parts by mass, and even more preferably 3 to 20 parts by mass. Such an embodiment is preferable from the viewpoint of the modulus and mechanical strength of the obtained layer (X).

<Other ingredients>
The composition of the present embodiment contains a cross-linking agent other than the peroxide-based cross-linking agent (B), a cross-linking aid other than the cross-linking aid (C), a softening agent, an inorganic filler, a reinforcing agent, an antistatic agent, and a processing aid. It may further contain at least one selected from agents, activators, hygroscopic agents, antistatic agents, colorants, lubricants and thickeners. The composition of the present embodiment may further contain polymers other than the copolymer (A), such as elastomers and / or rubbers. Each component described below may be used alone or in combination of two or more.

<< Cross-linking agents other than peroxide-based cross-linking agent (B), cross-linking aids other than cross-linking aid (C) >>
A cross-linking agent other than the cross-linking agent (B) may be used in combination with the peroxide-based cross-linking agent (B). Examples of the cross-linking agent other than the cross-linking agent (B) include cross-linking agents generally used when cross-linking rubber, and examples thereof include sulfur-based compounds, phenolic resins, hydrosilicone-based compounds, amino resins, quinone, and the like. Examples thereof include derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, and isocyanate-based compounds.

Examples of the sulfur-based compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthium disulfide, and selenium dithiocarbamate.

When a sulfur-based compound is also used as the cross-linking agent in the composition of the present embodiment, the content of the sulfur-based compound is the copolymer (A) and other polymers (rubber, etc.) that require cross-linking and are blended as necessary. ) Is preferably 0.3 to 10 parts by mass, more preferably 0.5 to 7.0 parts by mass, and further preferably 0.7 to 5.0 parts by mass with respect to 100 parts by mass.

When a sulfur-based compound is also used as the cross-linking agent, it is preferable to use a vulcanization accelerator in combination. Examples of the sulfide accelerator 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, Thiazole-based sulphurization accelerator such as dibenzothiazil disulfide; guanidine-based sulphurization accelerator such as diphenylguanidine, triphenylguanidine, diorsotrilguanidine; aldehyde amine-based such as acetaldehyde / aniline condensate and butylaldehyde / aniline condensate. Sulfurization accelerator; imidazoline-based sulphurization accelerator such as 2-mercaptoimidazolin; thiourea-based sulphurization accelerator such as diethylthiourea and dibutylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram Thiuram-based sulfide accelerators such as disulfide and dipentamethylene thiuram tetrasulfide; dithioate-based sulfide accelerators such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, telluryl diethyldithiocarbamate; ethylenethiourea ( For example, thiourea-based sulfide accelerators such as Sunseller 22C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), N, N'-diethylthiourea, N, N'-dibutylthiourea; and zantate-based such as zinc dibutylxatogenate. Sulfenamide accelerator; in addition, zinc flower can be mentioned.

When the composition of the present embodiment contains a vulcanization accelerator, the content of the vulcanization accelerator is the copolymer (A) and, if necessary, another polymer (rubber, etc.) that needs to be crosslinked. It is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and further preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total.

The vulcanization aid can be preferably used when a sulfur-based compound is also used as the cross-linking agent. For example, zinc oxide (for example, ZnO # 1, zinc oxide 2 type, manufactured by HakusuiTech Co., Ltd.), magnesium oxide, zinc oxide (for example, zinc oxide). , "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.) and the like zinc oxide).

When the composition of the present embodiment contains a vulcanization aid, the content of the vulcanization aid is the copolymer (A) and, if necessary, other polymer (rubber, etc.) that needs to be crosslinked. It is preferably 1 to 20 parts by mass with respect to 100 parts by mass in total.

Further, a cross-linking aid other than the cross-linking aid (C) may be used in combination with the cross-linking aid (C). Examples of the cross-linking aid include sulfur; a quinone-dioxime-based cross-linking aid such as p-quinone-dioxime; zinc oxide (for example, ZnO # 1 and zinc oxide 2 types (JIS standard (K-1410))), Huxuitec. Metal oxides such as magnesium oxide and zinc oxide (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)) can be mentioned.

When the composition of the present embodiment contains a cross-linking aid other than the cross-linking aid (C), the content of the cross-linking aid other than the cross-linking aid (C) is 1 mol of the peroxide-based cross-linking agent (B). On the other hand, it is preferably 0.5 to 10 mol, more preferably 0.5 to 7 mol, and further preferably 1 to 5 mol.

《Softener》
Examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; Fatroleum-based softeners such as soybean oil and coconut oil; waxes such as beeswax and carnauba wax; fatty acids such as ricinolic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or salts thereof; Or its derivatives; synthetic polymer substances such as terpene resin, petroleum resin, kumaron inden resin; ester-based softeners such as dioctylphthalate and dioctyl adipate; and other microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthesis Examples thereof include lubricating oil, tall oil, and sub (factis), and petroleum-based softeners are preferable, and process oils are more preferable.

When the composition of the present embodiment contains a softening agent, the content of the softening agent is 100 parts by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. On the other hand, it is preferably 2 to 100 parts by mass, and more preferably 5 to 100 parts by mass.

《Inorganic filler》
Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay. Among these, heavy calcium carbonate is preferable.
When the composition of the present embodiment contains an inorganic filler, the content of the inorganic filler is 100% by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. It is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass with respect to the parts.

《Reinforcing agent》
Examples of the reinforcing agent include silica, calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid, except for the carbon black (D) described above.
When the composition of the present embodiment contains a reinforcing agent, the content of the reinforcing agent is 100 parts by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. On the other hand, it is preferably 0.1 to 100 parts by mass, and more preferably 5 to 30 parts by mass.

<< Anti-aging agent (stabilizer) >>
By containing the anti-aging agent (stabilizer) in the composition of the present embodiment, the life of the layer (X) formed from the composition can be extended. Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

Examples of the amine-based anti-aging agent include aromatic secondary amine-based anti-aging agents such as phenylbutylamine and N, N-di-2-naphthyl-p-phenylenediamine. Examples of the phenolic anti-aging agent include dibutylhydroxytoluene and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. Examples of the sulfur-based anti-aging agent include thioether-based anti-aging agents such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide; nickel dibutyldithiocarbamate and the like. Dithiocarbamate-based anti-aging agents; 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate and the like.

When the composition of the present embodiment contains an anti-aging agent, the content of the anti-aging agent is 100% by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. It is preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 7.0 parts by mass with respect to parts.

《Processing aid》
As the processing aid, those generally blended in rubber as a processing aid can be widely used. Examples of the processing aid include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, and esters. Of these, stearic acid is preferred.

When the composition of the present embodiment contains a processing aid, the content of the processing aid is a total of 100% by mass of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. It is preferably 10 parts by mass or less, more preferably 8.0 parts by mass or less with respect to parts.

《Activator》
Activators include, for example, amines such as di-n-butylamine, dicyclohexylamine, monoeranolamine; zinc compounds of diethylene glycol, polyethylene glycol, lecithin, trialilute melilate, aliphatic carboxylic acid or aromatic carboxylic acid. Activators; zinc peroxide modifiers; octadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds.

When the composition of the present embodiment contains an activator, the content of the activator is 100 parts by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) to be blended as needed. On the other hand, it is preferably 0.2 to 10 parts by mass, and more preferably 0.3 to 5 parts by mass.

《Humidifier》
Examples of the hygroscopic agent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.
When the composition of the present embodiment contains a hygroscopic agent, the content of the hygroscopic agent is 100 parts by mass in total of the copolymer (A) and other polymers (elastomer, rubber, etc.) blended as needed. On the other hand, it is preferably 0.5 to 15 parts by mass, and more preferably 1.0 to 12 parts by mass.

《Other polymers》
The composition of the present embodiment can further contain a polymer other than the copolymer (A). Examples of other polymers that require cross-linking 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. Be done. Other polymers that do not require cross-linking include, for example, block copolymers of styrene and butadiene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-poly (ethylene-propylene) -polystyrene ( Polystyrene-based thermoplastic elastomer (TPS) such as SEPS), olefin-based thermoplastic elastomer (TPO), vinyl chloride-based elastomer (TPVC), ester-based thermoplastic elastomer (TPC), amide-based thermoplastic elastomer (TPA), urethane-based heat Examples thereof include elastomers such as plastic elastomer (TPU) and other thermoplastic elastomers (TPZ).

When the composition of the present embodiment contains another polymer, the content of the other polymer is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the copolymer (A). Is.

<Preparation of composition>
The composition of the present embodiment can be prepared by kneading each of the above-mentioned components at a desired temperature using, for example, a kneader such as a mixer, a kneader, or a roll.

The composition of this embodiment is prepared, for example, as follows. The copolymer (A) and a predetermined other component are put into a kneader and kneaded under predetermined heating conditions (for example, 80 to 200 ° C. for 3 to 30 minutes) to homogenize (A kneading). In the A kneading, a cross-linking agent or the like that crosslinks the copolymer (A) when heated to the heating temperature of the A kneading is not added. The temperature of the mixture kneaded in A kneading was then lowered to less than the cross-linking temperature of the peroxide-based cross-linking agent (B) (for example, 130 ° C. or lower), and then the peroxide-based cross-linking not added in A kneading was performed. Agent (B), cross-linking aid (C) and the like are added to the above mixture and further kneaded under predetermined heating conditions (for example, at a roll temperature of 30 to 80 ° C. for 1 to 30 minutes) to homogenize (Knead B). The composition of the embodiment can be obtained.

In the composition of the present embodiment, in the composition (A kneading) before blending the cross-linking agent, the Mooney viscosity ML _{(1 + 4) at} 100 ° C. is usually 10 to 250, preferably 10 to 100, more preferably. It is 10 to 70. A composition having a Mooney viscosity in the above range exhibits good post-treatment quality and has excellent rubber characteristics.

<Layer (X)>
A layer (X) can be obtained from the composition of this embodiment. The composition of the present embodiment can be molded by a thermoforming method such as extrusion molding, injection molding, press molding, calender molding, transfer molding, or foam molding. In the present embodiment, the crosslinking temperature of the composition is usually 140 ° C. or higher, preferably 150 to 220 ° C., and more preferably 160 to 200 ° C. Moreover, this cross-linking reaction can be carried out in air.

For example, the composition of the present embodiment has a high adhesive force suitable for molding processability and is excellent in processability. Further, by using the composition of the present embodiment, it is possible to produce a laminate excellent in high rubber elasticity, abrasion resistance, heat resistance, cold resistance and light weight.

[Specific example of laminated body]
In the laminate of the present embodiment, for example, an uncrosslinked layer made of the composition of the present embodiment described above is laminated on the fiber base material layer (Y), and if necessary, pressure is applied to crosslink and bond the composition. By performing the above, the layer (X) can be formed on the fiber base material layer (Y) and manufactured. The cross-linking conditions of the composition are as described above.

The laminate of the present embodiment has excellent adhesiveness (peeling strength) between the layer (X) and the fiber base material layer (Y), and further has abrasion resistance, heat resistance, cold resistance, mechanical strength, and rubber. Excellent elasticity. The laminate of this embodiment is useful, for example, as a belt. However, the laminate of the present embodiment is not limited to belt applications.

One embodiment of the belt has a laminate of this embodiment. Examples of the belt include transmission belts such as V-belts, flat belts, round belts, toothed belts, and V-ribbed belts; light transport belts, cylindrical belts, rough top belts, flanged transport belts, and U-shaped guides. Examples thereof include a transport belt such as a transport belt and a transport belt with a V guide.

In the present embodiment, the laminated body can be suitably used as a constituent member of the transmission belt. The transmission belt is, for example, a transmission belt for automobiles, a transmission belt for motorcycles, and a transmission belt for general industrial machines. Examples of the V-belt include a wrapped belt and a low-edge belt.

Further, the laminated body of the present embodiment can be suitably used as a constituent member of a handrail for an escalator. That is, the escalator handrail has the laminated body of the present embodiment.
Hereinafter, an embodiment of the transmission belt will be described. One embodiment of the transmission belt may have, for example, an adhesive rubber portion in which a core wire is embedded, and further may have a bottom rubber portion formed on the lower surface of the adhesive rubber portion. The transmission belt may have an upper canvas formed on the adhesive rubber portion and / or a lower canvas formed under the bottom rubber portion, if necessary. The transmission belt includes a laminate having a layer (X) corresponding to an adhesive rubber portion and / or a bottom rubber portion and a fiber base material layer (Y) corresponding to an upper canvas and / or a lower canvas.

The core wire, which is a tension member of the transmission belt, extends in the longitudinal direction of the belt at the adhesive rubber portion. Examples of the core wire include a polyester cord. The adhesive rubber portion surrounds the core wire and is adhered to the core wire. In one embodiment, for example, the composition of the present embodiment is arranged around the core wire and crosslinked to form an adhesive rubber portion adhered to the core wire.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass".
[Example 1]
Using MIXTRON BB MIXER (manufactured by Kobe Steel, BB-2 type, volume 1.7 L, rotor 2WH), 5 parts of ZnO # 1 as a cross-linking aid for 100 parts of Mitsui EPT 4045M, processing assistance 1 part of stearic acid as an agent, 2 parts of Irganox 1010 as an anti-aging agent, 4 parts of Sandant MB as an anti-aging agent, 50 parts of Asahi # 60UG as a carbon black, and 10 parts of PS-430 as a softening agent. After blending in an amount, kneading was performed to obtain Formulation 1. The kneading conditions at the time of preparing the formulation 1 were a rotor rotation speed of 40 rpm, a floating weight pressure of 3 kg / cm ² , a kneading time of 5 minutes, and a kneading discharge temperature of 144 ° C.

Next, after confirming that the temperature of the formulation 1 reached 40 ° C., 6.8 parts of DCP-40C (40% by mass of dicumyl peroxide) as a cross-linking agent was added to the formulation 1 using a 6-inch roll. As a cross-linking aid, Sun Ester EG was added in a blending amount of 2 parts and kneaded to obtain Formulation 2. The kneading conditions at the time of preparing the formulation 2 are that the roll temperature is the front roll / rear roll = 50 ° C./50 ° C., the roll peripheral speed is the front roll / rear roll = 18 rpm / 15 rpm, and the roll gap is 3 mm, and the kneading time is 8 minutes. The mixture was divided into two to obtain the formulation 2.

The compound 2 was pressed at 170 ° C. for 15 minutes using a press molding machine to prepare a crosslinked sheet having a thickness of 2 mm. The obtained crosslinked sheet was subjected to a hardness test, a tensile test, a heat aging test and a DIN friction test, which will be described later.

After confirming that the temperature of the formulation 1 was 40 ° C., 6.8 parts of DCP-40C (40% by mass of dicumyl peroxide) was added to the formulation 1 as a cross-linking agent using a 6-inch roll. As a cross-linking aid, Sun Ester EG was added in two parts and kneaded, and the roll temperature was set to front roll / rear roll = 50 ° C / 50 ° C, and the roll peripheral speed was set to front roll / rear roll. = 18 rpm / 15 rpm, the roll gap was 3 mm, and the mixture was dispensed into a sheet with a kneading time of 8 minutes to obtain a 3 mm thick uncrosslinked sheet.

An uncrosslinked sheet having a thickness of 3 mm was placed on a woven fabric of 6,6-nylon fiber (manufactured by Teijin Shoji Co., Ltd.) and pressed at 170 ° C. for 15 minutes using a 150-ton press molding machine. In this way, a crosslinked rubber-fiber base material laminate was obtained.

[Comparative Example 1]
A compound, a crosslinked sheet, an uncrosslinked sheet, and a crosslinked rubber-fiber base material laminate were obtained in the same manner as in Example 1 except that the type and amount of each compounding agent were as shown in Table 2.
The materials used in Examples and Comparative Examples are shown in Table 1 below.

<Vulcanization rate>
A vulcanization curve is measured using MDR2000 (manufactured by Alpha Technologies), and the minimum torque value S'min [dNm] and the maximum torque value S'max [dNm] and the minimum torque value S'min obtained from the vulcanization curve are measured. S'max-S'min and the time [min]: tc90 when the torque of the measurement sample reached 90% were determined with 0% and the maximum value S'max as 100%. The measurement conditions were a temperature of 170 ° C. and a time of 15 minutes. The smaller the tc90, the faster the vulcanization rate.

[Hardness test (Duro-A)]
The flat portions of the crosslinked sheet having a thickness of 2 mm were overlapped to form a sheet having a thickness of 12 mm, and the hardness (Duro-A) was measured according to JIS K6253.

[Tensile test: modulus, tensile breaking point stress, tensile breaking point elongation]
The above-mentioned crosslinked sheet having a thickness of 2 mm was punched out to prepare a No. 3 dumbbell test piece described in JIS K6251 (1993), and this test piece was used in accordance with the method specified in JIS K6251 Clause 3. Tensile tests were performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min, and tensile stresses (100% modulus (M100), 200% modulus (M200)) when the elongation rates were 100%, 200% and 300%. 300% modulus (M300)), tensile breaking point stress (TB) and tensile breaking point elongation (EB) were measured.

[Heat resistance test (heat aging test)]
The crosslinked sheet having a thickness of 2 mm was subjected to a heat aging test in which the crosslinked sheet was held at 180 ° C. for 70 hours according to JIS K6257. The hardness, TB and EB of the sheet after the heat aging test were measured by the same method as the items of the hardness test and the tensile test.
AH (Duro-A) was obtained from the difference in hardness before and after the heat aging test, and the rate of change after the test from TB and EB before and after the heat aging test with respect to the value before the heat aging test was calculated as Ac (TB) and Ac, respectively. Obtained as (EB).

[Emblittlement test]
The crosslinked sheet having a thickness of 2 mm was punched out to prepare a No. 3 dumbbell test piece described in JIS K6251 (2001). Using this test piece, the embrittlement temperature was derived according to the method specified in JIS K6261 (2006).

[DIN friction test (DIN wear amount)]
From the crosslinked sheet having a thickness of 2 mm, a disk-shaped test piece having a diameter of 16.0 ± 0.2 mm and a thickness of 6 mm or more was prepared in accordance with JIS-K6264-2: 2005. For this test piece, a DIN wear tester was used to rotate a drum with a diameter of 150.0 ± 0.2 mm and a length of 500 mm at 40 times / minute, and with a load of 1 kgf, the wear distance was 40.0 ± 0.2 m. The amount of wear (DIN wear amount: unit mm ³ ) was measured.

[Peeling test]
A test piece having a width of 25 mm was punched out from the obtained crosslinked rubber-fiber base material laminate, and a T-peeling test was performed at a tensile speed of 50 mm / min.

Claims (9)

Ethylene / α-olefin / non-conjugated polyene copolymer having a structural unit derived from ethylene (a1), a structural unit derived from α-olefin (a2), and a structural unit derived from non-conjugated polyene (a3). (A) and
Peroxide-based cross-linking agent (B) and
A layer (X) formed from a composition containing a cross-linking aid (C) having two or more ethylenic double bonds, and a layer (X).
It has a fiber base layer (Y) and
A laminate in which the layer (X) and the fiber base material layer (Y) are in contact with each other. The laminate according to claim 1, wherein the non-conjugated polyene (a3) comprises at least one selected from 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB). The laminate according to claim 1 or 2, wherein the α-olefin (a2) is propylene. The laminate according to any one of claims 1 to 3, wherein the fiber base material layer (Y) is a fiber base material containing fibers made of polyamide. A belt having the laminate according to any one of claims 1 to 4. The belt according to claim 5, which is a transmission belt or a transport belt. The belt according to claim 6, wherein the transmission belt is a V-belt, a flat belt, a round belt, a toothed belt, or a V-ribbed belt. The belt according to claim 6, wherein the transport belt is a light transport belt, a cylindrical belt, a rough top belt, a flanged transport belt, a U-shaped guided transport belt, or a V-guided transport belt. An escalator handrail having the laminate according to any one of claims 1 to 4.