JP2021175768A - Coating material - Google Patents

Abstract

To provide a coating material having excellent flexibility, wear resistance and impact resistance.SOLUTION: A coating material includes a composition comprising a copolymer composed of conjugated diene units and non-conjugated olefin units, with the content of butylene units being 0 mol%.SELECTED DRAWING: None

Description

The present invention relates to a coating material.

Since polyethylene has excellent electrical insulation and water resistance, it is used as a coating material for electric wires, cables, etc., and studies on additives based on the usage environment (see, for example, Patent Document 1), various polyethylenes (For example, see Patent Document 2) and the like.

Japanese Unexamined Patent Publication No. 2006-249136 Japanese Unexamined Patent Publication No. 1-129047

However, in the resin materials shown in Patent Documents 1 and 2, there is room for study in terms of wear resistance and impact resistance as a coating material.
An object of the present invention is to provide a coating material having excellent flexibility, abrasion resistance and impact resistance, and an object of the present invention is to solve the object.

<1> A coating material using a composition containing a copolymer containing a conjugated diene unit and a non-conjugated olefin unit and having a butylene unit content of 0 mol%.

<2> The coating material according to <1>, which further contains an olefin resin.
<3> The coating material according to <2>, wherein the olefin resin contains a non-conjugated olefin unit.
<4> The coating material according to <2> or <3>, wherein the olefin resin contains an olefin unit having 2 to 5 carbon atoms.
<5> The difference between the carbon number of the non-conjugated olefin unit contained in the copolymer and the carbon number of the non-conjugated olefin unit contained in the olefin resin is 2 or less in <3> or <4>. The covering material described.

<6> In the copolymer, the content of the conjugated diene unit is more than 0 mol% and 50 mol% or less, and the content of the non-conjugated olefin unit is 50 mol% or more and less than 100 mol% <1> to <5. > The covering material according to any one of.

<7> The coating material according to any one of <1> to <6>, wherein the copolymer further contains an aromatic vinyl unit.
<8> The copolymer has a content of the conjugated diene unit of 1 to 50 mol%, a content of the non-conjugated olefin unit of 40 to 97 mol%, and a content of the aromatic vinyl unit of 2. The coating material according to <7>, which is ~ 35 mol%.

<9> The coating material according to any one of <1> to <8>, wherein the copolymer has a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter.
<10> The coating material according to any one of <1> to <9>, wherein the copolymer has a crystallinity of 0.5 to 50%.
<11> The coating material according to any one of <1> to <10>, wherein the copolymer has a polystyrene-equivalent weight average molecular weight of 10,000 to 9,000,000.

<12> The coating material according to any one of <1> to <11>, wherein the copolymer is a non-conjugated olefin unit in which the non-conjugated olefin unit is acyclic.
<13> The coating material according to <12>, wherein the copolymer is composed of only ethylene units as the acyclic non-conjugated olefin unit.
<14> The coating material according to any one of <7> to <13>, wherein the copolymer contains a styrene unit in the aromatic vinyl unit.
<15> The copolymer according to any one of <1> to <14>, wherein the copolymer contains at least one selected from the group in which the conjugated diene unit consists of 1,3-butadiene units and isoprene units. Covering material.
<16> The coating material according to any one of <1> to <15>, wherein the copolymer has only an acyclic structure in the main chain.

According to the present invention, it is possible to provide a coating material having excellent flexibility, abrasion resistance and impact resistance.

<Coating material>
The coating material of the present invention is made by using a composition containing a copolymer containing a conjugated diene unit and a non-conjugated olefin unit and a content of a butylene unit of 0 mol%.
Hereinafter, the copolymer containing a conjugated diene unit and a non-conjugated olefin unit will be referred to as "the copolymer of the present invention".

The coating material using a polyethylene resin or the like was excellent in electrical insulation and water resistance, but had insufficient strength and impact resistance.
On the other hand, the coating material of the present invention contains the copolymer of the present invention. Since the copolymer contains a conjugated diene unit and is more flexible than a polyethylene-based resin, the coating material of the present invention is excellent in abrasion resistance and impact resistance (particularly low temperature impact resistance).

[Copolymer of the present invention]
The composition in the present invention contains a copolymer containing a conjugated diene unit and a non-conjugated olefin unit, and the content of the butylene unit is 0 mol%.
The copolymer of the present invention may be a binary copolymer composed of two units of a conjugated diene unit and a non-conjugated olefin unit, and further, a ternary composed of three units including an aromatic vinyl unit. It may be a copolymer, or may be a multiple copolymer containing a monomer unit other than the butylene unit.
For example, as the hydrogenated styrene / butadiene / styrene copolymer elastomer used in JP2012-246366, a hydrogenated styrene-ethylene / butylene-styrene copolymer (SEBS) containing a butylene unit is used. There is. The copolymer of the present invention has a butylene unit content of 0 mol%, and the copolymer of the present invention does not contain SEBS.

(Conjugated diene unit)
The conjugated diene unit is a structural unit derived from the conjugated diene compound as a monomer.
Here, the conjugated diene compound refers to a conjugated diene compound. The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of such conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compound may be used alone or in combination of two or more.

The conjugated diene compound as the monomer of the copolymer of the present invention is at least one selected from the group consisting of 1,3-butadiene and isoprene from the viewpoint of improving the mechanical strength and impact resistance of the coating material. , More preferably consisting of at least one selected from the group consisting of 1,3-butadiene and isoprene, and even more preferably consisting of only 1,3-butadiene.
In other words, the conjugated diene unit in the copolymer of the present invention preferably contains at least one selected from the group consisting of 1,3-butadiene units and isoprene units, and the 1,3-butadiene units and It is more preferably composed of at least one selected from the group consisting of isoprene units, and even more preferably composed of only 1,3-butadiene units.

When the copolymer of the present invention is a binary copolymer, the content of the conjugated diene unit is preferably more than 0 mol% and 50 mol% or less. In this case, a copolymer having excellent elongation and weather resistance can be obtained. From the same viewpoint, the ratio of conjugated diene units in the binary copolymer is more preferably 40 mol% or less.

In the binary copolymer, the ratio of 1,2 adducts (including 3,4 adducts) of conjugated diene units is preferably 10% or less. When the above ratio is 10% or less, the heat resistance and bending fatigue resistance of the copolymer of the present invention can be improved. From the same viewpoint, the ratio of 1,2 adducts (including 3,4 adducts) of conjugated diene units in the binary copolymer is more preferably 8% or less, further preferably 6% or less. The ratio of 1, 2 adducts (including 3, 4 adducts) of the conjugated diene unit is the ratio in the entire conjugated diene unit, not the ratio in the entire copolymer of the present invention. Further, the above ratio has the same meaning as the amount of 1,2-vinyl bond when the conjugated diene unit is a butadiene unit.

When the copolymer of the present invention is a ternary copolymer or a multidimensional copolymer, the content of the conjugated diene unit is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 mol% or more. It is more preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less.
When the content of the conjugated diene unit is 1 to 50 mol% of the total copolymer of the present invention, the flexibility, mechanical strength and impact resistance of the coating material can be improved.
From the viewpoint of further improving the flexibility, mechanical strength and impact resistance of the coating material, the content of the conjugated diene unit is preferably in the range of 1 to 50 mol% of the entire copolymer of the present invention, and is 5 to 40 mol%. The range is more preferable, and the range of 10 to 30 mol% is further preferable.

(Non-conjugated olefin unit)
The non-conjugated olefin unit is a structural unit derived from the non-conjugated olefin compound as a monomer.
Here, the non-conjugated olefin compound refers to an aliphatic unsaturated hydrocarbon having one or more carbon-carbon double bonds. The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of such non-conjugated olefin compounds include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, vinyl pivalate and 1-phenylthioethane. , N-vinylpyrrolidone and other heteroatomic substituted alkene compounds and the like. The non-conjugated olefin compound may be one kind alone or a combination of two or more kinds.

The non-conjugated olefin compound as a monomer of the copolymer of the present invention is a non-cyclic non-conjugated olefin compound from the viewpoint of improving the mechanical strength and impact resistance of the coating material and facilitating repair. The acyclic non-conjugated olefin compound is more preferably α-olefin, further preferably α-olefin containing ethylene, and particularly preferably composed of ethylene alone.
In other words, the non-conjugated olefin unit in the copolymer of the present invention is preferably an acyclic non-conjugated olefin unit, and the acyclic non-conjugated olefin unit is an α-olefin unit. More preferably, it is more preferably an α-olefin unit containing an ethylene unit, and particularly preferably it is composed of only an ethylene unit.

When the copolymer of the present invention is a binary copolymer, the content of the non-conjugated olefin unit is preferably 50 mol% or more and less than 100 mol%. In this case, the fracture characteristics of the coating material at high temperature can be effectively improved. From the same viewpoint, the proportion of non-conjugated olefin units in the binary copolymer is more preferably 60 mol% or more.

When the copolymer of the present invention is a ternary copolymer or a multidimensional copolymer, the content of the non-conjugated olefin unit is preferably 40 mol% or more, more preferably 45 mol% or more, and 55 mol. % Or more is more preferable, 60 mol% or more is particularly preferable, 97 mol% or less is preferable, 95 mol% or less is more preferable, and 90 mol% or less is further preferable. When the content of the non-conjugated olefin unit is 40 to 97 mol% of the total copolymer of the present invention, the mechanical strength and impact resistance of the coating material can be improved, and repair can be facilitated.
From the viewpoint of further improving the mechanical strength and impact resistance of the coating material and facilitating repair, the content of the non-conjugated olefin unit is preferably in the range of 40 to 97 mol% of the entire copolymer of the present invention. The range of 45 to 95 mol% is more preferable, the range of 55 to 90 mol% is further preferable, and the range of 60 to 90 mol% is further preferable.

(Aromatic vinyl unit)
The copolymer of the present invention preferably further contains an aromatic vinyl unit.
The aromatic vinyl unit is a structural unit derived from an aromatic vinyl compound as a monomer.
When the copolymer of the present invention contains an aromatic vinyl unit, it cleaves a plasma component such as an ethylene crystal component and suppresses excessive crystallization derived from a non-conjugated olefin unit, so that the copolymer of the present invention can be used. While improving the rigidity, the elasticity is not easily impaired, and high crack resistance can be obtained.
Here, the aromatic vinyl compound refers to an aromatic compound substituted with at least a vinyl group, and is not included in the conjugated diene compound. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Examples of such aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. .. The aromatic vinyl compound may be used alone or in combination of two or more.

The aromatic vinyl compound as the monomer of the copolymer of the present invention preferably contains styrene, and more preferably contains only styrene, from the viewpoint of improving the mechanical strength and impact resistance of the coating material. In other words, the aromatic vinyl unit in the copolymer of the present invention preferably contains a styrene unit, and more preferably consists of only a styrene unit.
The aromatic ring in the aromatic vinyl unit is not included in the main chain of the copolymer of the present invention unless it is bonded to an adjacent unit.

When the copolymer of the present invention is a ternary copolymer or a multidimensional copolymer, the content of the aromatic vinyl unit is preferably 2 mol% or more, more preferably 3 mol% or more, and more preferably. It is preferably 35 mol% or less, more preferably 30 mol% or less, and further preferably 25 mol% or less. When the content of the aromatic vinyl unit is 2 to 35 mol% of the total copolymer of the present invention, the mechanical strength and impact resistance of the coating material can be improved.
From the viewpoint of further improving the mechanical strength and impact resistance of the coating material, the content of the aromatic vinyl unit is preferably in the range of 2 to 35 mol% of the entire copolymer of the present invention, and is in the range of 3 to 30 mol%. More preferably, the range of 3 to 25 mol% is further preferable.

The content of other structural units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit is 30 mol% or less of the total copolymer of the present invention from the viewpoint of obtaining the desired effect of the present invention. It is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably not contained, that is, the content is 0 mol%. That is, the copolymer of the present invention is a binary copolymer composed of two units of a conjugated diene unit and a non-conjugated olefin unit, or three of a conjugated diene unit, a non-conjugated olefin unit and an aromatic vinyl unit. It is preferably a ternary copolymer consisting of units.

From the viewpoint of improving the mechanical strength and impact resistance of the coating material, the copolymer of the present invention has only one type of conjugated diene compound, only one type of non-conjugated olefin compound, and one type of aromatic vinyl as monomers. It is preferably a polymer obtained by polymerizing using at least a compound.
In other words, the copolymer of the present invention is preferably a copolymer containing only one kind of conjugated diene unit, only one kind of non-conjugated olefin unit, and only one kind of aromatic vinyl unit. More preferably, it is a ternary copolymer consisting of only conjugated diene units, only one non-conjugated olefin unit, and only one aromatic vinyl unit, with 1,3-butadiene units, ethylene units, and styrene units. It is more preferable that it is a ternary copolymer composed of only. Here, "only one type of conjugated diene unit" includes conjugated diene units having different binding modes.

When the copolymer of the present invention is a binary copolymer, the content of the conjugated diene unit is more than 0 mol% and 50 mol% or less, and the content of the non-conjugated olefin unit is 50 mol% or more and less than 100 mol%. Is preferable.
When the copolymer of the present invention is a ternary copolymer, the content of the conjugated diene unit is 1 to 50 mol%, the content of the non-conjugated olefin unit is 40 to 97 mol%, and the aromatic vinyl unit is used. The content is preferably 2-35 mol%.

The copolymer of the present invention preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 9,000,000 (10 to 9,000 kg / mol), and is preferably 100,000 to 8,000. It is more preferable to be 000 (100 to 8,000 kg / mol). When the Mw of the copolymer of the present invention is 10,000 or more, the mechanical strength and impact resistance of the coating material can be sufficiently ensured, and the Mw is 9,000,000 or less. Therefore, the workability of the composition is not easily impaired.

The copolymer of the present invention preferably has a polystyrene-equivalent number average molecular weight (Mn) of 10,000 to 1,000,000 (10 to 10,000 kg / mol), and is preferably 50,000 to 9,000. It is more preferably 000 (50 to 9,000 kg / mol), and even more preferably 100,000 to 8,000,000 (100 to 8,000 kg / mol). When the Mn of the copolymer of the present invention is 10,000 or more, the mechanical strength and impact resistance of the coating material can be sufficiently ensured, and the Mn is 10,000,000 or less. Therefore, the workability of the composition is not easily impaired.

The copolymer of the present invention preferably has a molecular weight distribution [Mw / Mn (weight average molecular weight / number average molecular weight)] of 1.00 to 4.00, and more preferably 1.00 to 3.50. It is preferably 1.80 to 3.00, and more preferably 1.80 to 3.00. When the molecular weight distribution of the copolymer of the present invention is 4.00 or less, sufficient homogeneity can be brought about in the physical properties of the copolymer of the present invention.

The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the copolymer of the present invention are determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The copolymer of the present invention preferably has an endothermic peak energy of 10 to 150 J / g, more preferably 30 to 120 J / g, as measured by a differential scanning calorimetry (DSC) at 0 to 120 ° C. When the heat absorption peak energy of the copolymer of the present invention is 10 J / g or more, the crystallinity of the copolymer of the present invention is high, and the crack resistance of the coating material can be improved. Further, when the endothermic peak energy of the copolymer of the present invention is 150 J / g or less, the workability of the composition is improved.
The endothermic peak energy of the copolymer of the present invention is raised from −150 ° C. to 150 ° C. at a heating rate of, for example, 10 ° C./min in accordance with JIS K 7121-1987 using a differential scanning calorimeter. And measure it.

The copolymer of the present invention preferably has a melting point of 30 to 130 ° C., more preferably 30 to 110 ° C., as measured by a differential scanning calorimeter (DSC). When the melting point of the copolymer of the present invention is 30 ° C. or higher, the crystallinity of the copolymer of the present invention is high, and the crack resistance of the coating material can be improved. Further, when the melting point of the copolymer of the present invention is 130 ° C. or lower, the workability of the composition is improved.
The melting point of the copolymer of the present invention may be measured according to JIS K 7121-1987 using a differential scanning calorimeter.

The copolymer of the present invention preferably has a glass transition temperature (Tg) of 0 ° C. or lower, more preferably -100 to −10 ° C., as measured by a differential scanning calorimeter (DSC). When the glass transition temperature of the copolymer of the present invention is 0 ° C. or lower, the mechanical strength and impact resistance of the coating material can be further improved.
The glass transition temperature of the copolymer of the present invention may be measured using a differential scanning calorimeter according to JIS K 7121-1987.

The copolymer of the present invention preferably has a crystallinity of 0.5 to 50%, more preferably 3 to 45%, and even more preferably 5 to 45%. When the crystallinity of the copolymer of the present invention is 0.5% or more, the crystallinity of the copolymer due to the non-conjugated olefin unit is sufficiently ensured, and the mechanical strength and impact resistance of the coating material are secured. Can be further improved. Further, when the crystallinity of the copolymer of the present invention is 50% or less, the workability and extrusion processability at the time of kneading the composition are improved.
The crystallinity of the copolymer of the present invention is determined by measuring the crystal melting energy of polyethylene, which is a 100% crystalline component, and the melting peak energy of the copolymer of the present invention, and the energy ratio between polyethylene and the copolymer of the present invention. From this, the degree of crystallinity may be calculated. In addition, the melting peak energy can be measured with a differential scanning calorimeter.

The copolymer of the present invention preferably has a main chain consisting only of an acyclic structure. Thereby, the mechanical strength and impact resistance of the covering material can be further improved.
In addition, NMR is used as a main measuring means for confirming whether or not the main chain of the copolymer of the present invention has a cyclic structure. Specifically, when a peak derived from the cyclic structure existing in the main chain (for example, a peak appearing at 10 to 24 ppm for a three-membered ring to a five-membered ring) is not observed, the main chain of the copolymer is determined. It is shown that it consists only of a non-cyclic structure.
In the present invention, the main chain of the polymer means a linear molecular chain in which all other molecular chains (long molecular chain, short molecular chain, or both) are connected like a pendant ["". See Section 1.34 of Glossary of Basic Terms in Polymer Science IUPAC Recommendations 1996, Pure Appl. Chem., 68, 2287-2311 (1996)]
Further, the copolymer of the present invention may have either a linear structure or a branched structure, but a linear structure is preferable.

The copolymer of the present invention is excellent in mechanical strength, specifically, excellent breaking strength, stepping strength, tensile strength, abrasion resistance, crack resistance and the like. The copolymer of the present invention is also excellent in mechanical strength at low temperatures.
Further, since the copolymer of the present invention has excellent mechanical strength without relying on a filler such as carbon black or silica, it can be colored with a colorant and has excellent decorativeness. On the other hand, since the copolymer of the present invention can interact with the filler, the filler can be used to further improve the mechanical strength.
Since the copolymer of the present invention contains a conjugated diene unit, it can be crosslinked, and the crosslink rate is the same as that of the diene rubber. Since the copolymer of the present invention contains a conjugated diene unit, it acts as an elastic body and can expand and contract. Since the copolymer of the present invention can be injection molded and stretched, it can be processed into a film. Since the copolymer of the present invention contains a conjugated diene unit and a non-conjugated olefin unit, it can easily adhere to both an olefin resin and a rubber, and therefore can function as an adhesive between the olefin resin and the rubber. The copolymer of the present invention can be foamed. The copolymer of the present invention preferably has a melting point of 30 to 130 ° C., and its shape can be restored by pouring hot water at about 80 to 100 ° C. or heating by immersing it in hot water. In addition, the copolymer of the present invention has shape memory characteristics.

When producing a binary copolymer composed of two units, a conjugated diene unit and a non-conjugated olefin unit, as the copolymer of the present invention, a polymerization step using the conjugated diene compound and the non-conjugated olefin compound as monomers is performed. After that, the copolymer of the present invention can be produced.
When a ternary copolymer composed of three units of a conjugated diene unit, a non-conjugated olefin unit and an aromatic vinyl unit is produced as the copolymer of the present invention, the conjugated diene compound, the non-conjugated olefin compound and the aromatic are produced. The copolymer of the present invention can be produced through a polymerization step using a vinyl compound as a monomer.

The method for producing a copolymer of the present invention may further undergo a coupling step, a washing step, and other steps, if necessary.
Hereinafter, the method for producing the copolymer of the present invention will be described on behalf of the case of producing the ternary copolymer.

In the production of the polymer, it is preferable that only the non-conjugated olefin compound and the aromatic vinyl compound are added without adding the conjugated diene compound in the presence of the polymerization catalyst, and these are first polymerized. In particular, when the catalyst composition described below is used, the conjugated diene compound is more reactive than the non-conjugated olefin compound and the aromatic vinyl compound. Therefore, the non-conjugated olefin compound and the aromatic compound are present in the presence of the conjugated diene compound. It is difficult to polymerize either or both of the group vinyl compounds. Further, it is also liable to be difficult due to the characteristics of the catalyst to first polymerize the conjugated diene compound and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound.

As the polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase massive polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. When a solvent is used in the polymerization reaction, the solvent may be any solvent that is inert in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

The polymerization step may be carried out in one step or in multiple steps of two or more steps.
The one-step polymerization step is all kinds of monomers to be polymerized, namely conjugated diene compounds, non-conjugated olefin compounds, aromatic vinyl compounds, and other monomers, preferably conjugated diene compounds, non-conjugated. This is a step of simultaneously reacting an olefin compound and an aromatic vinyl compound to polymerize them.
In the multi-step polymerization step, a part or all of one or two kinds of monomers are first reacted to form a polymer (first polymerization step), and then added in the first polymerization step. This is a step of polymerizing by performing one or more steps (second polymerization step to final polymerization step) of adding and polymerizing a type of monomer that has not been polymerized, the remainder of the monomer added in the first polymerization step, and the like. .. In particular, in the production of the copolymer of the present invention, it is preferable to carry out the polymerization step in multiple steps.

In the polymerization step, the polymerization reaction is preferably carried out in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of -100 ° C. to 200 ° C., and may be about room temperature. The pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound into the polymerization reaction system.
The reaction time of the polymerization reaction is also not particularly limited, and is preferably in the range of 1 second to 10 days, but can be appropriately selected depending on conditions such as the type of polymerization catalyst and the polymerization temperature.
Further, in the polymerization step of the conjugated diene compound, the polymerization may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

The polymerization step is preferably carried out in multiple steps. More preferably, the first step of mixing the first monomer raw material containing at least an aromatic vinyl compound with the polymerization catalyst to obtain a polymerization mixture, and the conjugated diene compound, the non-conjugated olefin compound and the polymerization mixture with respect to the polymerization mixture. It is preferable to carry out the second step of introducing the second monomer raw material containing at least one selected from the group consisting of aromatic vinyl compounds. Further, it is more preferable that the first monomer raw material does not contain the conjugated diene compound and the second monomer raw material contains the conjugated diene compound.

The first monomer raw material used in the first step may contain a non-conjugated olefin compound together with the aromatic vinyl compound. In addition, the first monomer raw material may contain the entire amount of the aromatic vinyl compound used, or may contain only a part of the aromatic vinyl compound. Further, the non-conjugated olefin compound is contained in at least one of the first monomer raw material and the second monomer raw material.

The first step is preferably carried out in the reactor under the atmosphere of an inert gas, preferably nitrogen gas or argon gas. The temperature (reaction temperature) in the first step is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, and may be about room temperature. The pressure in the first step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the aromatic vinyl compound into the polymerization reaction system. The time (reaction time) spent in the first step can be appropriately selected depending on the conditions such as the type of polymerization catalyst and the reaction temperature. For example, when the reaction temperature is 25 to 80 ° C., it is 5 minutes. The range of ~ 500 minutes is preferable.

In the first step, as the polymerization method for obtaining the polymerization mixture, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase massive polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Can be used. When a solvent is used in the polymerization reaction, the solvent may be any solvent that is inert in the polymerization reaction, and examples thereof include toluene, cyclohexanone, and normal hexane.

The second monomer raw material used in the second step is only the conjugated diene compound, or the conjugated diene compound and the non-conjugated olefin compound, or the conjugated diene compound and the aromatic vinyl compound, or the conjugated diene compound and the non-conjugated olefin compound. And aromatic vinyl compounds are preferred.
When the second monomer raw material contains at least one selected from the group consisting of a non-conjugated olefin compound and an aromatic vinyl compound in addition to the conjugated diene compound, these monomer raw materials are used as a solvent or the like in advance. It may be introduced into the polymerization mixture after being mixed with the compound, or each monomer raw material may be introduced from a single state. Further, each monomer raw material may be added at the same time or sequentially.
In the second step, the method of introducing the second monomer raw material into the polymerization mixture is not particularly limited, but the flow rate of each monomer raw material is controlled and continuously added to the polymerization mixture. It is preferable to do (so-called metering). Here, when a monomer raw material that is a gas under the conditions of the polymerization reaction system (for example, ethylene as a non-conjugated olefin compound under the conditions of room temperature and normal pressure) is used, the polymerization reaction system is carried out at a predetermined pressure. Can be introduced in.

The second step is preferably carried out in the reactor under the atmosphere of an inert gas, preferably nitrogen gas or argon gas. The temperature (reaction temperature) in the second step is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, and may be about room temperature. When the reaction temperature is raised, the selectivity of cis-1,4 bond in the conjugated diene unit may decrease. The pressure in the second step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate a monomer such as a conjugated diene compound into the polymerization reaction system. The time (reaction time) spent in the second step can be appropriately selected depending on the conditions such as the type of polymerization catalyst and the reaction temperature, but is preferably in the range of 0.1 hour to 10 days, for example.
Further, in the second step, the polymerization reaction may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

Here, in the polymerization step of the above-mentioned conjugated diene compound, non-conjugated olefin compound, and aromatic vinyl compound, various monomers are used as catalyst components in the presence of one or more of the following components (a) to (f). It is preferable to include a step of polymerizing. In the polymerization step, it is preferable to use one or more of the following components (a) to (f), but it is possible to combine two or more of the following components (a) to (f) and use them as a catalyst composition. More preferred.
(A) Component: Rare earth element compound or reaction product of the rare earth element compound and Lewis base (b) Component: Organic metal compound (c) Component: Aluminoxane (d) Component: Ionic compound (e) Component: Halogen compound ( f) Ingredients: substituted or unsubstituted cyclopentadiene (compound having a cyclopentadiene group), substituted or unsubstituted inden (compound having an indenyl group), and substituted or unsubstituted fluorene (compound having a fluorenyl group). ), The cyclopentadiene skeleton-containing compound (a) to (f) can be used in the polymerization step by referring to, for example, International Publication No. 2018/092733.

The coupling step is a step of performing a reaction (coupling reaction) for modifying at least a part (for example, a terminal) of the polymer chain of the copolymer obtained in the polymerization step.
In the coupling step, it is preferable to carry out the coupling reaction when the polymerization reaction reaches 100%.
The coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a tin-containing compound such as bis (-1-octadecyl maleate) dioctyltin (IV); 4 , 4'-Isocyanate compounds such as diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.
Among these, bis (-1-octadecyl maleate) dioctyltin (IV) is preferable in terms of reaction efficiency and low gel formation.
By carrying out the coupling reaction, the number average molecular weight (Mn) of the copolymer can be increased.

The washing step is a step of washing the copolymer obtained in the polymerization step.
The medium used for cleaning is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol and isopropanol. When a catalyst derived from Lewis acid is used as the polymerization catalyst. Can be used by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid, etc.) to these solvents. The amount of acid to be added is preferably 15 mol% or less with respect to the solvent. When the addition amount is 15 mol% or less, the acid is less likely to remain in the copolymer and is less likely to adversely affect the reaction during kneading and vulcanization of the composition.
By this washing step, the amount of catalyst residue in the copolymer can be suitably reduced.

The content of the copolymer of the present invention in the composition is preferably 10 to 100% by mass, preferably from the viewpoint of the flexibility of the coating material, mechanical strength, impact resistance, ease of repair, and the like. It is more preferably ~ 100% by mass, further preferably 51 to 100% by mass, and even more preferably 70 to 100% by mass.

[Olefin resin]
The coating material of the present invention preferably further contains an olefin resin.
When the coating material of the present invention contains an olefin resin, the abrasion resistance and impact resistance of the coating material can be further improved as compared with the case where the composition contains only the copolymer of the present invention.
The olefin resin may be contained in the composition [referred to as the composition (c)] containing the copolymer of the present invention, or may be contained in the composition (r) separately from the composition (c). It may be. It is assumed that the composition (r) does not contain the copolymer of the present invention. That is, the content of the copolymer of the present invention in the composition (r) is 0% by mass.
When the coating material contains the composition (c) containing the copolymer of the present invention and the composition (r) containing an olefin resin, the composition (where mechanical strength and impact resistance are not required) A coating material can be produced which is composed of the region (R) consisting of r) and is composed of the region (C) consisting of the composition (c) only in the portion where mechanical strength and impact resistance are required.

The olefin-based resin refers to a resin in which at least polyolefin has crystallinity and forms the main component of the resin. For example, an olefin-α-olefin copolymer, an olefin copolymer and the like may be mentioned and modified.
Specifically, polyethylene, ethylene-propylene copolymer, ethylene-hexene copolymer, ethylene-pentene copolymer, ethylene-octene copolymer, propylene-1-hexene copolymer, ethylene-4-methyl- Penten copolymer, propylene-4-methyl-1pentene copolymer, ethylene-butene copolymer, propylene-butene copolymer, 1-butene-hexene copolymer, 1-butene-4-methyl-pentene Polymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate Copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-methacrylic acid Examples thereof include polymers such as butyl copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, and propylene-vinyl acetate copolymer.

The olefin resin preferably contains a non-conjugated olefin unit. When the olefin resin contains a non-conjugated olefin unit, the adhesiveness and adhesion between the region (C) and the region (R) are enhanced, and the coating material is pulled or an external load is applied to the coating material. In addition, the region (C) and the region (R) are integrally pulled or deformed, and cracks are unlikely to occur.
From the viewpoint of further enhancing the integrity of the region (C) and the region (R), the olefin resin preferably contains an olefin unit having 2 to 5 carbon atoms, and further contains the copolymer of the present invention. The difference between the number of carbon atoms of the non-conjugated olefin unit and the number of carbon atoms of the non-conjugated olefin unit contained in the olefin resin is preferably 2 or less.
The copolymer of the present invention and the olefin resin contain a non-conjugated olefin unit which is a common unit, and the non-conjugated olefin unit has a similar structure, so that the region (C) and the region (R) can be separated from each other. Adhesiveness is further improved. As a result, when the covering material is pulled or bent, the region (C) having elasticity and flexibility follows the region (R), and the covering material is less likely to crack and has mechanical strength. It also has excellent impact resistance.

The difference between the carbon number of the non-conjugated olefin unit contained in the copolymer of the present invention and the carbon number of the non-conjugated olefin unit contained in the olefin resin is more preferably 1 or less, and preferably 0. More preferred. Further, the carbon number of the olefin unit is more preferably 2 to 4, and more preferably 2 to 3, that is, a polyethylene resin and a polypropylene resin are further preferable.

The polyethylene-based resin means a polymer containing an ethylene unit as a main component (for example, more than 50 mol%) in the main chain, and may further contain other units such as a propylene unit. Further, the polyethylene-based resin may be thermosetting or thermoplastic. Specific examples thereof include polyethylene (homogeneous polymer) and ethylene-propylene copolymer (however, ethylene unit is more than 50 mol%).
Further, the polyethylene-based resin includes types such as ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE). However, any of them may be used.

Among these, from the viewpoint of high versatility, it is preferable to use one or more polyethylene-based resins selected from the group consisting of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE).

The polypropylene-based resin means a polymer containing a propylene unit as a main component (for example, more than 50 mol%) in the main chain, and may further contain other units such as an ethylene unit. Further, the polypropylene-based resin may be thermosetting or thermoplastic. Specific examples thereof include polypropylene (homogeneous polymer) and ethylene-propylene copolymer (however, the propylene unit is more than 50 mol%).

From the viewpoint of improving the mechanical strength and impact resistance of the coating material, the polystyrene-equivalent number average molecular weight (Mn) of the olefin resin is preferably 5 to 10,000 kg / mol, preferably 7 to 1,000 kg. It is more preferably / mol, and even more preferably 10 to 1,000 kg / mol.

From the viewpoint of improving the mechanical strength and impact resistance of the coating material, the weight average molecular weight (Mw) of the olefin resin is preferably 100 to 300 kg / mol, more preferably 180 to 300 kg / mol, and 200 to 280 kg. / Mol is more preferable.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the olefin resin can be measured by gel permeation chromatography (GPC), for example, "HLC-8321GPC / HT" manufactured by Tosoh Corporation. GPC (Gel Permeation Chromatography) can be used

The content of the olefin resin in the composition (r) is preferably 10 to 90% by mass, preferably 30 to 90% by mass, from the viewpoint of the flexibility, mechanical strength and impact resistance of the coating material. More preferably, it is more preferably 51 to 100% by mass, and even more preferably 70 to 100% by mass.
The content of the olefin resin in the composition (c) is preferably 0 to 90% by mass, preferably 0 to 70% by mass, from the viewpoint of the flexibility, mechanical strength and impact resistance of the coating material. It is more preferably 0 to 49% by mass, further preferably 0 to 30% by mass.

When the coating material of the present invention contains the composition (r), the ratio of the composition (c) to the composition (r) in the coating material [mass of the composition (c)] / [of the composition (r) The mass] is selected according to the usage pattern of the covering material, and may be 9/1 to 1/9, 7/3 to 3/7, or 5/5.

The composition (c) may further contain a polymer component other than the copolymer and the olefin resin of the present invention, and various components generally used in the resin field and the rubber field, for example, a filler; Fibers; Anti-aging agents; Softeners; Stearic acid, Zinc flowers, Cross-linking packages containing cross-linking accelerators and cross-linking agents; Resins; UV absorbers; Foaming agents; It can be appropriately selected and blended within the range that does not occur. Commercially available products can be preferably used as these various components.
Further, the composition (r) may further contain a polymer component other than the copolymer and the olefin resin of the present invention, and also contains various components generally used in the resin field and the rubber field. May be good.

Examples of the polymer component other than the olefin resin include resins other than the olefin resin, an elastomer, a rubber component and the like.

[Resin, elastomer]
Examples of resins and elastomers other than olefin resins include polyamide resins; polyester thermoplastic elastomers; polyester resins such as polybutylene terephthalate and polybutylene naphthalate. Only one kind of these may be used, or two or more kinds may be used.

[Rubber component]
Examples of the rubber component include diene-based rubbers such as natural rubber (NR) and synthetic diene-based rubbers.
Specific examples of the synthetic diene rubber include polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), chloroprene rubber (CR), butyl halide rubber, and acryloni little-butadiene. Examples include rubber (NBR).
As the diene rubber, one type may be used alone, or two or more types may be used. Further, the diene rubber may be modified.
The rubber component may include non-diene rubber.

[Various ingredients]
(filler)
Examples of the filler include carbon black and an inorganic filler.
When the composition contains a rubber component, the mechanical strength and impact resistance of the vulcanized rubber can be improved by further containing a filler, and the mechanical strength and impact resistance of the coating material can be improved. Can be done.
The type of carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF, and SAF, and HAF, ISAF, and SAF are preferable.
Examples of the inorganic filler include metal oxides such as silica, alumina, and titania, and silica is particularly preferable. The type of silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), and colloidal silica. When silica is contained as a filler, the composition may further contain a silane coupling agent in order to improve the dispersibility of silica in the composition of the present invention.

(Anti-aging agent)
Examples of the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds and phosphorus compounds.

(Softener)
Softeners include petroleum-based softeners such as process oils, lubricating oils, naphthenic oils, paraffins, liquid paraffins, petroleum asphalt, and vaseline, fatty oil-based softeners such as castor oil, flaxseed oil, rapeseed oil, and palm oil, and honey. Examples thereof include waxes such as wax, carnauba wax, and lanolin. These softeners may be used alone or in combination of two or more.

(Crosslinking agent)
The cross-linking agent is not particularly limited, and examples thereof include peroxides, sulfur, oximes, amines, and ultraviolet curing agents.
Since the copolymer of the present invention contains a conjugated diene unit, it can be crosslinked (vulcanized) with sulfur. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.

(Crosslink accelerator)
When the composition of the present invention contains a rubber component, a cross-linking accelerator (vulcanization accelerator) may be contained in order to promote vulcanization of the rubber component.
Examples of the vulcanization accelerator include guadinin type, sulfenamide type, thiuram type, thiazole type, aldehyde amine type, thiocarbamate type and the like.

[Method for producing composition (c)]
The composition (c) may be produced by using the copolymer of the present invention as it is, or by mixing any additive component in addition to the copolymer of the present invention.
In addition, the copolymer of the present invention is kneaded alone or in combination with any other additive component using a kneader such as a single-screw extrusion kneader, a twin-screw extrusion kneader, a Banbury mixer, a roll, or an internal mixer. May be manufactured.
As each component to be blended in the production of the composition (c), it is preferable to blend the amount indicated as the content of each component in the composition (c) as the blending amount.
The kneading of each component may be carried out in one step, or may be divided into two or more steps.

When the components of the composition (c) are melt-kneaded by an extrusion kneader and the composition (c) is extruded, the extruded composition may be directly cut into pellets or after forming strands. , The strands may be cut with a pelletizer into pellets. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere.

[Manufacturing method of coating material]
The coating material of the present invention may be produced by the composition (c) alone, or the composition (c) and the composition (r) may be melt-kneaded and then extruded, or the composition (c) alone may be produced. Alternatively, it may be produced by hot-pressing the composition (c) and the composition (r).
The hot press temperature is preferably 120 to 160 ° C, more preferably 130 to 150 ° C.
A foaming agent may be added to each composition to form a foaming type coating material, or the surface of the coating material may be subjected to a solvent, or the surface may be treated by electron beam irradiation, microwave irradiation, or the like.

The coating material of the present invention is useful as a coating material for various conducting wires such as electric wires, telephone lines, and LAN cables.
For example, an electric wire is usually placed in an environment exposed to rain for a long period of time, and in a cold region, a hard splatter or a sharp splatter may hit due to a blizzard. Even in such a case, since the electric wire is covered with the coating material of the present invention, it is possible to prevent the electric wire from being damaged and the metal wire from being exposed. Further, since the copolymer of the present invention is highly flexible, it does not hinder the flexibility of the cable even after the cable is coated with the coating material of the present invention. Further, since the two sheets made of the copolymer of the present invention are easily adhered to each other at a low temperature, even if the coating material is damaged by an external load, the coating material of the present invention is placed on the coating material. The dressing can be easily repaired by applying and heating.

Since the coating material of the present invention is excellent in mechanical strength and impact resistance, it can be used as a coating material for various products, not limited to the coating of conductors as described above. The mode of use of the covering material may be not only a mode of covering the entire product but also a partial coating covering only the required place.
The covering material of the present invention includes, for example, automobile parts (automobile seats, automobile batteries (lithium ion batteries, etc.), weather strips, hose tubes, anti-vibration rubbers, cables, sealing materials, etc.), marine parts, and the like. Suitable for coating building materials and the like.
In addition, the covering material of the present invention includes anti-vibration rubber, hose, resin piping, sound absorbing material, bedding, precision parts for office equipment (OA roller), bicycle frame, golf ball, tennis racket, golf shaft, medical equipment (medical treatment). Tubes, bags, microneedles, rubber sleeves, artificial organs, caps, packings, injector gaskets, medicine plugs, artificial legs, artificial limbs), cosmetics (containers), building materials (floor materials, anti-vibration rubber, seismic isolation rubber, building films) , Sound absorbing material, waterproof sheet, heat insulating material, joint material, sealing material), packaging material, liquid crystal material, organic EL material, organic semiconductor material, electronic material, electronic device, communication equipment, aircraft parts, mechanical parts, electronic parts, agriculture Materials, textiles (wearable base), daily necessities (toothbrush, shoe sole, glasses, artificial bait, binoculars, toys, dust masks, garden hoses), robot parts, optical parts, road materials (asphalt, guard rails, poles, signs), It is suitable for protective equipment (shoes, safety shoes for stepping prevention, bulletproof gaskets), exterior parts for electrical equipment, OA exterior parts, soles, sealing materials, and the like.
In the above, LAN means Local Area Network, OA means office automation, UV means ultraviolet, and EL means electro-luminescence.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not limit the present invention in any way.

<Ingredients>
Copolymer (P1): Three-way copolymer copolymer produced by the following production method (P2): Three-way copolymer copolymer produced by the following production method (P101): SEBS sheet, manufactured by Asahi Kasei Co., Ltd. Product name "Tough Tech"
Olefin resin (LLDPE): Linear low density polyethylene, manufactured by Ube-Maruzen Polyethylene, trade name "Umerit 0540F"

[Production of copolymer (P1)]
82 g of styrene and 680 g of toluene were added to a fully dried 2000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, 0.037 mmol of mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex 1,3-[ (T-Bu) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ], 0.037 mmol dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] Was charged, and 25 g of toluene was added to prepare a catalytic solution. The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 60 ° C.

Next, ethylene was charged into the pressure-resistant stainless steel reactor at a pressure of 0.7 MPa, and copolymerization was carried out at 75 ° C. for a total of 2 hours. Continuously 2 g / min. 240 g of toluene solution containing 60 g of 1,3-butadiene was added at the rate of.
Then, 1 mL of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) was added to the pressure-resistant stainless steel reactor to terminate the reaction.
Then, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain a copolymer (P1).
The obtained copolymer (P1) had the physical characteristics shown in Table 1.

[Production of copolymer (P2)]
82 g of styrene and 680 g of toluene were added to a fully dried 2000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, 0.037 mmol of mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex 1,3-[ (T-Bu) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ], 0.037 mmol dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] Was charged, and 25 g of toluene was added to prepare a catalytic solution. The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 60 ° C.

Next, ethylene was charged into the pressure-resistant stainless steel reactor at a pressure of 0.7 MPa, and copolymerization was carried out at 75 ° C. for a total of 2 hours. Continuously 2 g / min. 240 g of toluene solution containing 60 g of 1,3-butadiene was added at the rate of.
Then, 1 mL of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) was added to the pressure-resistant stainless steel reactor to terminate the reaction.
Then, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain a copolymer (P2).
The obtained copolymer (P2) had the physical characteristics shown in Table 1.

^{Since no peak was observed at 10 to 24 ppm in the 13} C-NMR spectrum charts of the copolymers (P1) and (P2), it was confirmed that the main chain consisted only of an acyclic structure.
The physical properties of the copolymers (P1) and (P2) were measured by the following methods.

[Method for measuring physical properties of copolymers (P1) and (P2)]
(1) Number average molecular weight (Mn), weight average molecular weight (Mw), peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: HLC-8121 GPC / HT manufactured by Toso Co., Ltd., column: GMH _HR- H (S) HT x 2, manufactured by Toso Co., Ltd., detector: differential refractometer (RI)] to obtain monodisperse polystyrene. As a reference, the polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymer were determined. The measurement temperature is 40 ° C.

(2) Content of butadiene unit, ethylene unit, styrene unit The content (mol%) of ethylene unit, butadiene unit, and styrene unit in the copolymer can be determined by ^{1 1} H-NMR spectrum (100 ° C, d-tetrachloroethane standard). : 6 ppm) was calculated from the integration ratio of each peak.

(3) Melting point (Tm), glass transition temperature (Tg)
Using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000"), the melting point (Tm) and glass transition temperature (Tg) of the copolymer are compliant with JIS K 7121-1987. ) Was measured. In the DSC curve, when there are two peaks, the one with the lower melting point is shown as Tm-1 and the one with the higher melting point is shown in Table 1. When there was one peak, only Tm-1 was shown in Table 1.

(4) Crystallinity The copolymer sample was heated from −150 ° C. to 150 ° C. at 10 ° C./min, and the endothermic peak energy (ΔH ₁ ) of 0 to 100 ° C. at that time and 100 to 150 ° C. The endothermic peak energy (ΔH ₂ ) was measured.
Further, in the same manner, the crystal melting energy (ΔH ₀ ) of polyethylene having a 100% crystal component was measured.
From the ratio (ΔH ₁ / ΔH ₀ ) of the heat absorption peak energy (ΔH ₁ ) of the copolymer at 0 to 100 ° C. to the crystal melting energy (ΔH ₀ ) of the polyethylene, ethylene units (non-conjugated olefin) at 0 to 100 ° C. The degree of crystallinity (%) derived from the unit) is calculated, and the ratio (ΔH _{2 ) of the heat absorption peak energy (ΔH 2} ) of the copolymer at 100 to 150 ° C. to the _{crystal melting energy (ΔH 0) of the polyethylene is calculated.} From / ΔH ₀ ), the crystallinity (%) derived from the ethylene unit (non-conjugated olefin unit) at 100 to 150 ° C. was calculated.
The endothermic peak energy of the copolymer sample and the crystal melting energy of polyethylene were measured by a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000"). The results are shown in Table 1.

(5) Confirmation of main chain structure ¹³ C-NMR spectrum was measured for the synthesized copolymer.

<Manufacturing of coating material>
[Coating material 1]
The copolymer (P1) was hot-pressed at 145 ° C. to produce a P1 sheet having a thickness of 1 mm, which was used as a coating material 1.

[Coating material 2]
The copolymer (P2) was hot-pressed at 145 ° C. to produce a P2 sheet having a thickness of 1 mm, which was used as a coating material 2.

[Coating material 101]
The copolymer (P101) was hot-pressed at 145 ° C. to produce a P101 sheet having a thickness of 1 mm, which was used as a coating material 101.

[Coating material 102]
An olefin resin (LLDPE) was hot-pressed at 145 ° C. to produce a P102 sheet having a thickness of 1 mm, which was used as a coating material 102.

<Evaluation of dressing>
1. 1. Mechanical Strength The mechanical strength of the coating materials 1, 2, 101 and 102 was evaluated from the viewpoint of tensile strength (Tb; Tensile Strength at break) and elongation at break (Eb).
The covering materials 1, 2, 101 and 102 were formed into a dumbbell-shaped No. 3 shape based on JIS K 6251 (2017) to prepare a test piece.
Tensile strength (Tb) is required to stretch the test piece 100% at 25 ° C. and break the test piece using a tensile test device (manufactured by Instron) based on JIS K 6251 (2017). It was measured as the maximum tensile force.
The breaking elongation (Eb) is obtained by pulling the test piece at a speed of 100 mm / min at 25 ° C., measuring the length when the covering material breaks, and determining the length relative to the length before pulling (100%). rice field.
The results are shown in Table 2.

2. Cryogenic impact test The coating materials 1, 2, 101 and 102 were cut into a size of 100 mm × 100 mm in length and width to obtain a test piece. After cooling the test piece with liquid nitrogen, it was allowed to stand on a cork plate, and after 5 seconds, an iron ball weighing 500 g was dropped onto the test piece from a height of 30 cm.
The results are shown in Table 2.

As can be seen from Table 2, the coating materials 1 and 2 of the examples have a tensile strength of more than 30 MPa, excellent mechanical strength, a tensile elongation of more than 500% and excellent flexibility, and also break even in a low temperature impact test. However, it showed excellent low temperature impact resistance.
On the other hand, the covering material 101 of the comparative example had a low tensile strength and a low low temperature impact resistance. Further, although the covering material 102 of the comparative example had high tensile strength, low temperature impact resistance could not be obtained.
As described above, the covering material of the example is hard to break even if it receives a large external load, and even if it receives an impact in a low temperature environment, the covering material is only deformed and the fragments of the covering material are scattered. Can be avoided. Therefore, for example, the electric wire covered with the covering material of the embodiment can be used in a cold region, and the electric wire covered with the covering material can be protected even if it is hit by a hard substance scattered by a strong wind or the like.

3. 3. Puncture test The covering material 1, the covering material 101 and the covering material 102 were cut into a size of 100 mm × 100 mm in length and width to obtain a test piece. A round nail with a thickness of # 10 was fixed on the table so that the tip (convex side of the nail) protruded 10 mm from the table. The test piece was pressed against the tip of the nail and evaluated according to the following criteria.
◯: The hole did not penetrate.
X: The hole has penetrated.
The results are shown in Table 3.

As can be seen from Table 3, the covering material 1 of the example did not penetrate the hole, whereas the covering materials 101 and 102 of the comparative example penetrated the hole.
Therefore, for example, even if the electric wire covered with the covering material of the embodiment is used in a cold region and is hit by a sharp substance scattered by a strong wind or the like, the electric wire covered with the covering material is not damaged and an electric leakage occurs. Etc. can be prevented.

4. Abrasion test A test piece was obtained by cutting the covering material 2, the covering material 101 and the covering material 102 into a size of 10 mm × 100 mm in length and width. After measuring the mass (W0) of the test piece, the test piece was pressed against a rotating # 1000 file at a specified pressure (10 kPa) for 1 minute, and the mass (W1) of the test piece was measured again. The weight loss amount (W0-W1) of the test piece before and after the wear test was calculated.
The results are shown in Table 4.

As shown in Table 4, the covering material 2 of the example had a smaller amount of wear loss than the covering materials 101 and 102 of the comparative example. Therefore, even if the electric wires and the like coated with the covering material of the embodiment are bundled and rubbed, the electric wires and the like are not easily damaged, the scattering of the fragments of the covering material is suppressed, and the environmental pollution by the microplastic is suppressed. It is expected that

From the above results, the coating material of the example containing the copolymer in the present invention is rich in flexibility, has excellent mechanical strength equal to or higher than that of the coating material of the comparative example, and further has low temperature impact resistance. It turns out that is also excellent.

Claims (16)

A coating material using a composition containing a copolymer containing a conjugated diene unit and a non-conjugated olefin unit and having a butylene unit content of 0 mol%. The coating material according to claim 1, further comprising an olefin resin. The coating material according to claim 2, wherein the olefin resin contains a non-conjugated olefin unit. The coating material according to claim 2 or 3, wherein the olefin resin contains an olefin unit having 2 to 5 carbon atoms. The coating material according to claim 3 or 4, wherein the difference between the carbon number of the non-conjugated olefin unit contained in the copolymer and the carbon number of the non-conjugated olefin unit contained in the olefin resin is 2 or less. Any one of claims 1 to 5 in which the content of the conjugated diene unit is more than 0 mol% and 50 mol% or less, and the content of the non-conjugated olefin unit is 50 mol% or more and less than 100 mol%. The covering material described in the section. The coating material according to any one of claims 1 to 6, wherein the copolymer further contains an aromatic vinyl unit. The copolymer has a conjugated diene unit content of 1 to 50 mol%, a non-conjugated olefin unit content of 40 to 97 mol%, and an aromatic vinyl unit content of 2 to 35 mol%. The covering material according to claim 7. The coating material according to any one of claims 1 to 8, wherein the copolymer has a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter. The coating material according to any one of claims 1 to 9, wherein the copolymer has a crystallinity of 0.5 to 50%. The coating material according to any one of claims 1 to 10, wherein the copolymer has a polystyrene-equivalent weight average molecular weight of 10,000 to 9,000,000. The coating material according to any one of claims 1 to 11, wherein the copolymer is a non-conjugated olefin unit in which the non-conjugated olefin unit is acyclic. The coating material according to claim 12, wherein the copolymer is composed of only ethylene units as the acyclic non-conjugated olefin unit. The coating material according to any one of claims 7 to 13, wherein the copolymer contains a styrene unit as the aromatic vinyl unit. The coating material according to any one of claims 1 to 14, wherein the copolymer contains at least one of the conjugated diene units selected from the group consisting of 1,3-butadiene units and isoprene units. The coating material according to any one of claims 1 to 15, wherein the copolymer has only an acyclic structure in the main chain.