Molded articles, methods for hydrophilizing molded articles, composites, resin products, and rubber products

Abstract

To provide a molded article that achieves both excellent tensile strength and hydrophilicity. [Solution] In order to solve the above problems, the present invention provides a molded article comprising a conjugated diene-non-conjugated olefin copolymer having conjugated diene units and non-conjugated olefin units, characterized in that the contact angle between the surface of the molded article and water is 90° or less.

Description

Technical Field

[0001] The present invention relates to a molded body, a method for hydrophilizing a molded body, a composite, a resin product, and a rubber product.

Background Art

[0002] In various industries, products using polymers are manufactured. For example, low-density polyethylene, high-density polyethylene, polypropylene, polyvinyl chloride, and polystyrene are actively manufactured as the five major general-purpose resins and used as raw materials for molded bodies. Regarding polymers, when used as a molded body, various improvements such as polymer synthesis, modification, and surface treatment are being made in order to further impart desired functions according to their uses.

[0003] For example, as a polymer material excellent in durability such as tensile strength and various other properties, a copolymer obtained by polymerizing at least a conjugated diene compound and a non-conjugated olefin compound as monomers in the presence of a predetermined catalyst is known (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As described above, for a molded body made of a copolymer having a conjugated diene unit and a non-conjugated olefin unit disclosed in Patent Document 1, properties such as tensile strength can be improved. However, for example, when dyeing is performed or when used as a composite with a metal, further improvement in the hydrophilicity of the material has been desired.

[0006] Therefore, the present invention aims to solve the problems of the above-mentioned prior art and provide molded articles, composites, resin products, and rubber products that achieve both excellent tensile strength and hydrophilicity. Furthermore, the present invention aims to provide a method for hydrophilizing a molded article that has excellent tensile strength while also improving its hydrophilicity. [Means for solving the problem]

[0007] The gist of the present invention, which solves the above problems, is as follows. [1] A molded article comprising a conjugated diene-non-conjugated olefin copolymer having conjugated diene units and non-conjugated olefin units, A molded body characterized in that the contact angle between the surface of the molded body and water is 90° or less.

[0008] [2] The molded article according to [1], characterized in that the conjugated diene-non-conjugated olefin copolymer has a melting point of 50 to 120°C.

[0009] [3] The molded article according to [1] or [2], characterized in that the conjugated diene-non-conjugated olefin copolymer has a content of conjugated diene units that is greater than 0 mol% and less than or equal to 50 mol%, and a content of non-conjugated olefin units that is 50 mol% or more and less than 100 mol%.

[0010] [4] The molded article according to any one of [1] to [3], characterized in that the copolymer further contains aromatic vinyl units.

[0011] [5] A molded article according to any one of [1] to [4], further characterized by containing a resin component.

[0012] [6] The molded article according to [5], further characterized in that the resin component is at least one selected from the group consisting of olefin resins, polystyrene resins, and polyvinyl chloride resins.

[0013] [7] The molded body according to any one of [1] to [6], characterized in that the film thickness of the molded body is 10 μm to 2.0 mm.

[0014] [8] The molded body according to any one of [1] to [7], characterized in that the surface of the molded body is hydrophilic.

[0015] [9] A method for hydrophilizing the surface of a molded body containing a conjugated diene-non-conjugated olefin copolymer having a conjugated diene unit and a non-conjugated olefin unit, The method for hydrophilizing a molded body, characterized by including an oxidation step for the molded body.

[0016]

[10] The method for hydrophilizing a molded body according to [9], characterized in that the oxidation of the molded body includes a step of irradiating light on the surface of the molded body after bringing the molded body into contact with chlorine dioxide gas.

[0017]

[11] The method for hydrophilizing a molded body according to [9], characterized in that the oxidation of the molded body includes a step of bringing the molded body into contact with a gas obtained by irradiating chlorine dioxide gas with light.

[0018]

[12] A composite, characterized by comprising the molded body according to any one of [1] to [8] and a metal.

[0019]

[13] The composite according to

[11] , characterized in that the metal is in the form of a cord or a plate.

[0020]

[14] A rubber product using the molded body according to any one of [1] to [8], characterized in that the rubber product is a tire, a rubber crawler or a hose.

[0021]

[15] A resin product, characterized by using the molded body according to any one of [1] to [8].

Advantages of the Invention

[0022] According to the present invention, it is possible to provide a molded body, a composite, a resin product, and a rubber product in which excellent tensile strength and hydrophilicity are compatible. Further, according to the present invention, it is possible to provide a method for hydrophilizing a molded body that has excellent tensile strength and can also improve hydrophilicity.

Brief Description of the Drawings

[0023] [Figure 1] It is a diagram for explaining the mode of oxidation treatment with sodium chlorite and LED-UV light irradiation in the examples. (a) shows the outline of the apparatus, and (b) shows the state where the treatment sample is placed in the inner container of the glass double container.

Modes for Carrying Out the Invention

[0024] Hereinafter, the molded body, the method for hydrophilizing the molded body, the composite, the resin product, and the rubber product of the present invention will be exemplified and described in detail based on their embodiments.

[0025] The compounds described in this specification may be partially or entirely derived from fossil resources, may be derived from biological resources such as plant resources, or may be derived from recycled resources such as used tires. Further, it may be derived from a mixture of any two or more of fossil resources, biological resources, and recycled resources.

[0026] <Molded Body> The molded body of the present invention is a molded body containing a conjugated diene-non-conjugated olefin copolymer having a conjugated diene unit and a non-conjugated olefin unit, characterized in that the contact angle between the surface of the molded body and water is 90° or less.

[0027] By forming the molded body from a conjugated diene-non-conjugated olefin copolymer, excellent tensile strength can be obtained. Further, since the contact angle between the surface of the molded body and water is 90° or less, hydrophilicity can be enhanced, and as a result, it becomes possible to achieve both excellent tensile strength and hydrophilicity. Furthermore, the molded article of the present invention also has the effect of being easier to dye due to its increased surface hydrophilicity, and improved adhesion to metal materials.

[0028] Here, hydrophilization of the molded surface refers to a state in which the contact angle between the surface of the molded body and water is small, resulting in wettability. Specifically, the contact angle between the surface of the molded body and water is 90° or less, preferably 87° or less, more preferably 85° or less, even more preferably 83° or less, even more preferably 80° or less, and particularly preferably 77° or less. The contact angle between the surface of the molded body and water is not limited, but is preferably 30° or greater.

[0029] The method for making the surface of the molded body hydrophilic is not particularly limited. For example, this could involve incorporating a highly hydrophilic material into the material constituting the molded body, or applying a hydrophilic treatment to the surface of the molded body. Furthermore, the method for applying a hydrophilic treatment to the surface of the molded body could include, for example, a treatment that increases the reactivity of the surface of the molded body with water using a gas or liquid, or a treatment that increases the reactivity of the surface with water by applying physical pressure to the surface of the molded body. Among these methods, it is preferable to perform light irradiation after oxidizing the surface of the molded body to make it hydrophilic. This is because it allows for more reliable hydrophilication of the surface of the molded body.

[0030] Furthermore, the surface of the molded article of the present invention measured 1725 cm² when measured by IR. ‐1 It is preferable that the nearby carbonyl-derived peaks are broadly elevated.

[0031] The shape of the molded article of the present invention is not particularly limited and can be appropriately selected according to the required performance. For example, the molded article of the present invention can take on various shapes such as film-like, plate-like, rod-like, fibrous, or lump-like forms.

[0032] Furthermore, when the molded article of the present invention is in the form of a film or a plate, the film thickness is preferably 10 μm to 2.0 mm, more preferably 50 μm to 1.0 mm, and even more preferably 100 μm to 300 μm. When the film thickness of the molded article is 10 μm or more, it is possible to achieve both excellent tensile strength and hydrophilicity, and when the film thickness of the molded article is 2.0 mm or less, sufficient moldability can be ensured even when it is a composite of general-purpose resins, particularly at least one selected from the group consisting of olefin resins, polystyrene resins, and polyvinyl chloride resins, or other materials such as rubber components or metals. The thickness of the molded body refers to the value measured at the thickest part of the molded body.

[0033] (Conjugated diene-nonconjugated olefin copolymer) Furthermore, the molded article of the present invention includes a conjugated diene-non-conjugated olefin copolymer (hereinafter sometimes simply referred to as "polymer") having conjugated diene units and non-conjugated olefin units. This makes it possible to improve the tensile strength of the molded article. The copolymer having the conjugated diene unit and the non-conjugated olefin unit may be a binary copolymer consisting of two units, the conjugated diene unit and the non-conjugated olefin unit; it may also be a ternary copolymer consisting of three units, including an aromatic vinyl unit; or it may also be a polypolymer containing other monomer units.

[0034] -Conjugated diene units- The aforementioned conjugated diene unit is a constituent unit derived from a conjugated diene compound as a monomer. Here, the term "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, and 2,3-dimethyl-1,3-butadiene. The conjugated diene compound may be used alone or in combination of two or more types.

[0035] From the viewpoint of improving the tensile strength of the copolymer, the conjugated diene compound as a monomer of the copolymer preferably contains at least one selected from the group consisting of 1,3-butadiene and isoprene, more preferably consists of only at least one selected from the group consisting of 1,3-butadiene and isoprene, and even more preferably consists of only 1,3-butadiene. In other words, the conjugated diene units in the copolymer preferably include at least one selected from the group consisting of 1,3-butadiene units and isoprene units, more preferably consist only of at least one selected from the group consisting of 1,3-butadiene units and isoprene units, and even more preferably consist only of 1,3-butadiene units.

[0036] When the copolymer is a binary copolymer, the content of conjugated diene units is preferably greater than 0 mol% and less than or equal to 50 mol%. In this case, a copolymer with excellent elongation and weather resistance can be obtained. From a similar viewpoint, it is more preferable that the proportion of conjugated diene units in the binary copolymer is 40 mol% or less.

[0037] In a binary copolymer, the proportion of 1,2 adducts (including 3,4 adducts) of conjugated diene units is preferably 10 mol% or less. A proportion of 10 mol% or less improves the heat resistance and flexural fatigue resistance of the copolymer. Similarly, the proportion of 1,2 adducts (including 3,4 adducts) of conjugated diene units in a binary copolymer is more preferably 8 mol% or less, and even more preferably 6 mol% or less. Note that the proportion of 1,2 adducts (including 3,4 adducts) of conjugated diene units refers to the proportion of all conjugated diene units, not the proportion of the entire copolymer. Furthermore, when the conjugated diene units are butadiene units, this proportion has the same meaning as the amount of 1,2-vinyl bonds.

[0038] When the copolymer is a ternary copolymer or a polypolymer, the content of conjugated diene units is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 35 mol% or less. The flexibility and tensile strength of the copolymer can be improved by having a conjugated diene unit content of 1 to 50 mol% of the total copolymer. From the viewpoint of further improving the flexibility and tensile strength of the copolymer, the content of conjugated diene units is preferably in the range of 1 to 50 mol%, more preferably in the range of 3 to 40 mol%, and even more preferably in the range of 5 to 35 mol% of the total copolymer.

[0039] -Non-conjugated olefin units- The aforementioned non-conjugated olefin unit is a constituent unit derived from a non-conjugated olefin compound as a monomer. Here, a non-conjugated olefin compound refers to an aliphatic unsaturated hydrocarbon compound having one or more carbon-carbon double bonds. Preferably, the non-conjugated olefin compound 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, and heteroatom-substituted alkene compounds such as vinyl pivalate, 1-phenylthioethene, and N-vinylpyrrolidone. The non-conjugated olefin compound may be used alone or in combination of two or more types.

[0040] The non-conjugated olefin compound used as a monomer in the copolymer is preferably an acyclic non-conjugated olefin compound, from the viewpoint of improving the tensile strength of the copolymer and further facilitating retreading. The acyclic non-conjugated olefin compound is more preferably an α-olefin, even more preferably an α-olefin containing ethylene, and particularly preferably composed solely of ethylene. In other words, the non-conjugated olefin units in the copolymer are preferably acyclic non-conjugated olefin units, more preferably α-olefin units, even more preferably α-olefin units containing ethylene units, and particularly preferably consisting only of ethylene units.

[0041] When the copolymer is a binary copolymer, the content of non-conjugated olefin units is preferably 50 mol% or more and less than 100 mol%. In this case, the high-temperature fracture characteristics of the copolymer can be effectively improved. From a similar viewpoint, the proportion of non-conjugated olefin units in the binary copolymer is more preferably 60 mol% or more.

[0042] When the copolymer is a ternary copolymer or a polypolymer, the content of non-conjugated olefin units is preferably 40 mol% or more, more preferably 45 mol% or more, even more preferably 55 mol% or more, particularly preferably 60 mol% or more, and also preferably 97 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less. A non-conjugated olefin unit content of 40 to 97 mol% of the total copolymer improves the tensile strength of the copolymer and makes retreading easier. From the viewpoint of further improving the tensile strength of the copolymer and making retreading easier, the content of non-conjugated olefin units is preferably in the range of 40 to 97 mol%, more preferably in the range of 45 to 95 mol%, even more preferably in the range of 55 to 90 mol%, and still more preferably in the range of 60 to 90 mol% of the total copolymer.

[0043] -Aromatic vinyl units- The copolymer preferably further contains aromatic vinyl units. Aromatic vinyl units are constituent units derived from aromatic vinyl compounds as monomers. The presence of aromatic vinyl units in the copolymer allows for the cleavage of crystalline components such as ethylene crystals, suppressing excessive crystallization derived from non-conjugated olefin units. This improves the rigidity of the copolymer while minimizing the loss of elasticity, resulting in high crack resistance and thus enhancing the crack resistance of the copolymer. Here, an aromatic vinyl compound refers to an aromatic compound substituted with at least a vinyl group, and is not included in conjugated diene compounds. 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, and p-ethylstyrene. The aromatic vinyl compound may be used alone or in combination of two or more types.

[0044] The aromatic vinyl compound used as the monomer of the copolymer preferably contains styrene, and more preferably consists solely of styrene, from the viewpoint of improving the tensile strength of the copolymer. In other words, the aromatic vinyl units in the copolymer preferably contain styrene units, and more preferably consist solely of styrene units. Furthermore, the aromatic ring in an aromatic vinyl unit is not included in the main chain of the copolymer unless it is bonded to an adjacent unit.

[0045] When the copolymer is a ternary copolymer or a polypolymer, the aromatic vinyl unit content is preferably 2 mol% or more, more preferably 35 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less. Having an aromatic vinyl unit content of 2 to 35 mol% of the total copolymer improves the tensile strength of the copolymer. From the viewpoint of further improving the tensile strength of the copolymer, the content of aromatic vinyl units is preferably in the range of 2 to 35 mol%, more preferably in the range of 2 to 30 mol%, and even more preferably in the range of 2 to 25 mol% of the total copolymer.

[0046] From the viewpoint of obtaining the desired effects of the present invention, the content of other constituent units other than conjugated diene units, non-conjugated olefin units, and aromatic vinyl units is preferably 30 mol% or less of the total copolymer, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably none, i.e., 0 mol%. In other words, the copolymer is preferably a binary copolymer consisting of two units, a conjugated diene unit and a non-conjugated olefin unit, or a ternary copolymer consisting of three units, a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. Furthermore, from the viewpoint of reliably obtaining the desired effect, it is preferable that the copolymer has a butylene unit content of 0 mol%.

[0047] From the viewpoint of improving the tensile strength of the copolymer, it is preferable that the copolymer is a polymer obtained by polymerizing at least one type of conjugated diene compound, one type of unconjugated olefin compound, and one type of aromatic vinyl compound as monomers. In other words, the copolymer is preferably a copolymer containing only one type of conjugated diene unit, only one type of non-conjugated olefin unit, and only one type of aromatic vinyl unit; more preferably a ternary copolymer consisting only of one type of conjugated diene unit, only one type of non-conjugated olefin unit, and only one type of aromatic vinyl unit; and even more preferably a ternary copolymer consisting only of 1,3-butadiene units, ethylene units, and styrene units. Here, "only one type of conjugated diene unit" includes conjugated diene units with different bonding modes.

[0048] In the case of a binary copolymer, for example, it is preferable that the content of conjugated diene units is greater than 0 mol% and less than or equal to 50 mol%, and the content of unconjugated olefin units is greater than or equal to 50 mol% and less than 100 mol%. In this case, a copolymer with excellent elongation and weather resistance can be obtained, and the fracture characteristics of the copolymer at high temperatures can be effectively improved.

[0049] Furthermore, if the copolymer is, for example, a ternary copolymer, it is preferable that the content of conjugated diene units is 1 to 50 mol%, the content of unconjugated olefin units is 40 to 97 mol%, and the content of aromatic vinyl units is 2 to 35 mol%. In this case, the flexibility and tensile strength of the copolymer can be improved while further retreading can be facilitated.

[0050] -Physical properties of copolymers- The copolymer preferably has a number-average molecular weight (Mn) on a polystyrene basis of 10,000 to 9,000,000 (10 to 9,000 kg / mol), and more preferably 100,000 to 8,000,000 (100 to 8,000 kg / mol). A Mn of 10,000 or more ensures sufficient tensile strength of the copolymer, while a Mn of 9,000,000 or less makes it less likely to impair the workability of the copolymer itself or a composition containing the copolymer.

[0051] The copolymer preferably has a weight-average molecular weight (Mw) on a polystyrene basis of 10,000 to 10,000,000 (10 to 10,000 kg / mol), more preferably 50,000 to 9,000,000 (50 to 9,000 kg / mol), and even more preferably 100,000 to 8,000,000 (100 to 8,000 kg / mol). A Mw of 10,000 or more ensures sufficient tensile strength of the copolymer, while a Mw of 10,000,000 or less makes it less likely to impair the workability of the copolymer itself or a composition containing the copolymer.

[0052] The copolymer preferably has a molecular weight distribution [Mw / Mn (weight-average molecular weight / number-average molecular weight)] of 1.00 to 4.00, more preferably 1.00 to 3.50, and even more preferably 1.80 to 3.00. If the molecular weight distribution of the copolymer is 4.00 or less, sufficient homogeneity can be provided to the physical properties of the copolymer.

[0053] The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymer are determined by gel permeation chromatography (GPC) using polystyrene as the standard substance.

[0054] The copolymer preferably has an endothermic peak energy of 10 to 150 J / g, and more preferably 30 to 120 J / g, as measured by differential scanning calorimeter (DSC) at 0 to 120°C. If the endothermic peak energy of the copolymer is 10 J / g or higher, the crystallinity of the copolymer is increased, and the crack resistance of the copolymer can be improved. Furthermore, if the endothermic peak energy of the copolymer is 150 J / g or lower, the workability of the copolymer itself or the composition containing the copolymer is improved. The endothermic peak energy of the copolymer can be measured using a differential scanning calorimeter in accordance with JIS K 7121-1987, for example, by raising the temperature from -150°C to 150°C at a heating rate of 10°C / min.

[0055] The copolymer preferably has a melting point of 50 to 120°C, and more preferably 50 to 110°C. If the melting point of the copolymer is 50°C or higher, the crystallinity of the copolymer increases, and the crack resistance of the copolymer can be improved. If the melting point of the copolymer is 120°C or lower, the workability of the copolymer itself or the composition containing the copolymer improves. Furthermore, if the melting point of the copolymer is 50 to 120°C, the crack resistance of the copolymer is high, and the workability in the manufacture of the copolymer is improved. The melting point of the copolymer can be measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121-1987.

[0056] The copolymer preferably has a glass transition temperature (Tg) of 0°C or lower, as measured by differential scanning calorimeter (DSC), and more preferably -110°C to -10°C. If the glass transition temperature of the copolymer is 0°C or lower, the tensile strength of the copolymer can be further improved. The glass transition temperature of the copolymer can be measured using a differential scanning calorimeter in accordance with JIS K 7121-1987.

[0057] The copolymer preferably has a degree of crystallinity of 0.5 to 50%, more preferably 3 to 45%, and even more preferably 5 to 45%. If the degree of crystallinity of the copolymer is 0.5% or higher, sufficient crystallinity of the copolymer due to non-conjugated olefin units can be ensured, and the tensile strength of the copolymer can be further improved. Furthermore, if the degree of crystallinity of the copolymer is 50% or lower, the workability during kneading of the copolymer itself or a composition containing the copolymer, and the extrusion processability are improved. The degree of crystallinity of the copolymer can be determined by measuring the crystalline melting energy of 100% crystalline polyethylene and the melting peak energy of the copolymer, and calculating the degree of crystallinity from the energy ratio of polyethylene to copolymer. The melting peak energy can be measured using a differential scanning calorimeter.

[0058] Preferably, the copolymer's main chain consists solely of acyclic structures. This further improves the tensile strength of the copolymer. Furthermore, NMR is the primary measurement method used to confirm whether or not the main chain of the copolymer has a cyclic structure. Specifically, if no peaks originating from the cyclic structure present in the main chain (for example, peaks appearing at 10-24 ppm for three-membered to five-membered rings) are observed, it indicates that the main chain of the copolymer consists only of acyclic structures. In this specification, the main chain of a polymer refers to a linear molecular chain in which all other molecular chains (long or short molecular chains, or both) are linked together 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)]. Furthermore, the copolymer may have either a linear or branched structure, but a linear structure is preferred.

[0059] The copolymer exhibits excellent tensile strength, specifically superior fracture strength, puncture resistance, tensile strength, abrasion resistance, crack resistance, and impact resistance. The copolymer also exhibits excellent tensile strength at low temperatures. Furthermore, since the copolymer exhibits excellent tensile strength without relying on fillers such as carbon black or silica, it can be colored using colorants, resulting in excellent decorative properties. On the other hand, since the copolymer can interact with fillers, its tensile strength can be further improved by using fillers. The copolymer contains conjugated diene units and is therefore crosslinkable. The copolymer also contains conjugated diene units and acts as an elastic material, being stretchable and expandable. The copolymer can be injection molded and stretched, and can therefore be processed into a film. Because the copolymer contains conjugated diene units and non-conjugated olefin units, it readily adheres to both resins (olefin resins) and rubbers (diene-based rubbers), and can therefore function as an adhesive between resins and rubbers. Furthermore, the copolymer can be foamed. As described above, the copolymer preferably has a melting point of 50 to 120°C, and its shape can be restored by heating, such as by pouring hot water at about 80 to 100°C or immersing it in hot water. Furthermore, the copolymer has shape memory properties.

[0060] -Method of producing copolymers- When producing a binary copolymer consisting of two units, a conjugated diene unit and a non-conjugated olefin unit, the copolymer can be produced by a polymerization step using the conjugated diene compound and the non-conjugated olefin compound as monomers. Furthermore, when producing a ternary copolymer consisting of three units—a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit—the copolymer can be produced by a polymerization step using a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound as monomers.

[0061] The method for producing the copolymer may further involve a coupling step, a washing step, and other steps, as necessary. The following describes a method for producing a copolymer, using the case of producing a ternary copolymer as an example.

[0062] In the production of copolymers, it is preferable to add only the non-conjugated olefin compound and the aromatic vinyl compound in the presence of a polymerization catalyst, without adding the conjugated diene compound, and to polymerize them first. In particular, when using the catalyst composition described later, the conjugated diene compound is more reactive than the non-conjugated olefin compound and the aromatic vinyl compound, making it difficult to polymerize either or both of the non-conjugated olefin compound and the aromatic vinyl compound in the presence of the conjugated diene compound. Furthermore, polymerizing the conjugated diene compound first and then additionally polymerizing the non-conjugated olefin compound and the aromatic vinyl compound is also often difficult due to the characteristics of the catalyst.

[0063] Any polymerization method can be used, such as solution polymerization, suspension polymerization, liquid-phase bulk polymerization, emulsion polymerization, gas-phase polymerization, or solid-phase polymerization. Furthermore, if a solvent is used in the polymerization reaction, any solvent that is inert in the polymerization reaction is acceptable, such as toluene, cyclohexane, or n-hexane.

[0064] The polymerization process may be carried out in one step or in two or more steps. A single polymerization step is a step in which all types 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 olefin compounds, and aromatic vinyl compounds, are reacted and polymerized simultaneously. Furthermore, a multi-stage polymerization process is a process in which a polymer is formed by first reacting some or all of one or two types of monomers (first polymerization stage), and then polymerizing by adding monomers of the type not added in the first polymerization stage, the remainder of the monomers added in the first polymerization stage, etc., in one or more stages (second polymerization stage to final polymerization stage). In particular, it is preferable to carry out the polymerization process in multiple stages in the production of the copolymer.

[0065] In the polymerization process, the polymerization reaction is preferably carried out under an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The temperature of the polymerization reaction is not particularly limited, but for example, it is preferably in the range of -100°C to 200°C, and can also be around room temperature. Furthermore, 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. Furthermore, there are no particular restrictions on the reaction time of the polymerization reaction; for example, a range of 1 second to 10 days is preferred, but it can be appropriately selected depending on conditions such as the type of polymerization catalyst and polymerization temperature. Furthermore, during the polymerization process of the conjugated diene compound, polymerization may be stopped using polymerization inhibitors such as methanol, ethanol, or isopropanol.

[0066] The polymerization process is preferably carried out in multiple stages. More preferably, it is preferable to carry out a first step of mixing a first monomer raw material containing at least an aromatic vinyl compound with a polymerization catalyst to obtain a polymerization mixture, and a second step of introducing a second monomer raw material containing at least one selected from the group consisting of conjugated diene compounds, non-conjugated olefin compounds, and aromatic vinyl compounds into the polymerization mixture. Furthermore, it is even more preferable that the first monomer raw material does not contain a conjugated diene compound and the second monomer raw material contains a conjugated diene compound.

[0067] The first monomer raw material used in the first step may contain a non-conjugated olefin compound along with the aromatic vinyl compound. Furthermore, the first monomer raw material may contain the entire amount of the aromatic vinyl compound used, or only a portion of it. In addition, the non-conjugated olefin compound is contained in at least one of the first monomer raw material and the second monomer raw material.

[0068] The first step is preferably carried out in a reactor under the atmosphere of an inert gas, preferably nitrogen or argon. The temperature in the first step (reaction temperature) is not particularly limited, but for example, it is preferably in the range of -100°C to 200°C, and can also be around room temperature. The pressure in the first step is not particularly limited, but in order to sufficiently incorporate the aromatic vinyl compound into the polymerization reaction system, it is preferably in the range of 0.1 to 10.0 MPa. The time spent in the first step (reaction time) can be appropriately selected depending on the type of polymerization catalyst, reaction temperature, and other conditions, but for example, when the reaction temperature is 25 to 80°C, it is preferably in the range of 5 to 500 minutes.

[0069] In the first step, any polymerization method can be used to obtain the polymerization mixture, such as solution polymerization, suspension polymerization, liquid-phase bulk polymerization, emulsion polymerization, gas-phase polymerization, or solid-phase polymerization. Furthermore, if a solvent is used in the polymerization reaction, any solvent that is inert in the polymerization reaction is acceptable, such as toluene, cyclohexanone, or n-hexane.

[0070] The second monomer raw material used in the second step is preferably a conjugated diene compound alone, or a conjugated diene compound and a non-conjugated olefin compound, or a conjugated diene compound and an aromatic vinyl compound, or a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound. Furthermore, if the second monomer raw material includes at least one selected from the group consisting of a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound, these monomer raw materials may be mixed with a solvent beforehand and then introduced into the polymerization mixture, or each monomer raw material may be introduced individually. In addition, each monomer raw material may be added simultaneously or sequentially. In the second step, there are no particular restrictions on the method of introducing the second monomer raw material to the polymerization mixture, but it is preferable to control the flow rate of each monomer raw material and add it continuously to the polymerization mixture (so-called metering). Here, when using 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 conditions of room temperature and atmospheric pressure), it can be introduced into the polymerization reaction system at a predetermined pressure.

[0071] The second step is preferably carried out in a reactor under an inert gas atmosphere, preferably nitrogen gas or argon gas. The temperature in the second step (reaction temperature) is not particularly limited, but for example, a range of -100°C to 200°C is preferred, and it can also be around room temperature. Note that increasing the reaction temperature may decrease the selectivity of the cis-1,4 bond in the conjugated diene unit. The pressure in the second step is not particularly limited, but a range of 0.1 to 10.0 MPa is preferred in order to sufficiently incorporate monomers such as conjugated diene compounds into the polymerization reaction system. The time spent in the second step (reaction time) can be appropriately selected depending on conditions such as the type of polymerization catalyst and reaction temperature, but for example, a range of 0.1 hours to 10 days is preferred. Furthermore, in the second step, the polymerization reaction may be stopped using polymerization inhibitors such as methanol, ethanol, or isopropanol.

[0072] Here, the polymerization steps of the conjugated diene compound, unconjugated olefin compound, and aromatic vinyl compound described above preferably include a step of polymerizing the various monomers in the presence of one or more of the following components (a) to (f) as catalyst components. It is preferable to use one or more of the following components (a) to (f) in the polymerization step, but it is even more preferable to use a combination of two or more of the following components (a) to (f) as a catalyst composition. (a) Components: Rare earth element compounds or reaction products of said rare earth element compounds with Lewis bases (b) Component: Organometallic compound (c) Ingredients: Aluminoxane (d) Component: Ionic compound (e) Components: Halogen compounds (f) Components: Cyclopentadiene skeleton-containing compounds selected from substituted or unsubstituted cyclopentadiene (compounds having a cyclopentadienyl group), substituted or unsubstituted indene (compounds having an indenyl group), and substituted or unsubstituted fluorene (compounds having a fluorenyl group). The components (a) to (f) above can be used in the polymerization process, for example, by referring to International Publication No. 2018 / 092733, etc.

[0073] The coupling step is a step in which a reaction (coupling reaction) is carried out to modify at least a portion (for example, the ends) of the polymer chain of the copolymer obtained in the polymerization step. In the coupling process, it is preferable to perform the coupling reaction when the polymerization reaction reaches 100%. There are no particular restrictions on the coupling agent used in the coupling reaction, and it can be appropriately selected depending on the purpose. Examples include tin-containing compounds such as bis(1-octadecyl maleate) dioctyltin(IV); isocyanate compounds such as 4,4'-diphenylmethane diisocyanate; and alkoxysilane compounds such as glycidylpropyltrimethoxysilane. These may be used individually or in combination of two or more. Among these, bis(1-octadecyl maleate)dioctyltin(IV) is preferred in terms of reaction efficiency and low gel formation. Furthermore, the number-average molecular weight (Mn) of the copolymer can be increased by performing a coupling reaction.

[0074] The washing step is a process of washing the copolymer obtained in the polymerization step. There are no particular restrictions on the medium used for washing, and it can be appropriately selected depending on the purpose. Examples include methanol, ethanol, and isopropanol. However, when using a catalyst derived from a Lewis acid as a polymerization catalyst, an acid (e.g., hydrochloric acid, sulfuric acid, nitric acid, etc.) can be added to these solvents. The amount of acid added is preferably 15 mol% or less relative to the solvent. By adding 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. This washing process can effectively reduce the amount of catalyst residue in the copolymer.

[0075] (Other ingredients) Furthermore, the molded article of the present invention may contain polymer components other than the conjugated diene-non-conjugated olefin copolymer, as well as various compounding agents. Examples of polymer components include resin components and rubber components. Examples of compounding agents include fillers, reinforcing fibers, antioxidants, softeners, crosslinked packages containing stearic acid, zinc oxide, crosslinking promoters and crosslinking agents, resins, UV absorbers, foaming agents, and colorants.

[0076] The molded article of the present invention preferably further contains a resin component in order to enhance various properties such as wear resistance and impact resistance. Examples of the resin component include olefin resins, polystyrene resins, polyvinyl chloride resins, polyurethane resins, polyamide resins, polyester resins, and the like.

[0077] -Olefin resin- The molded article may contain an olefin resin. Here, copolymers having the conjugated diene units and non-conjugated olefin units are excluded from the olefin resin. The inclusion of an olefin resin in the molded article improves the wear resistance and impact resistance of the molded article.

[0078] The aforementioned olefin-based resin refers to a resin in which at least a polyolefin is crystalline and forms the main body of the resin. Examples include olefin-α-olefin copolymers, olefin copolymers, etc., which may be modified. Specifically, polyethylene, ethylene-propylene copolymer, ethylene-hexene copolymer, ethylene-pentene copolymer, ethylene-octene copolymer, propylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, propylene-4-methyl-1-pentene copolymer, ethylene-butene copolymer, propylene-butene copolymer, 1-butene-hexene copolymer, 1-butene-4-methyl-pentene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene Examples of polymers include 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-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, and propylene-vinyl acetate copolymer.

[0079] The olefin resin preferably contains non-conjugated olefin units. The inclusion of non-conjugated olefin units in the olefin resin makes the molded article less prone to cracking. The olefin resin preferably contains olefin units having 2 to 5 carbon atoms, and more preferably the difference between the number of carbon atoms in the non-conjugated olefin units contained in the copolymer and the number of carbon atoms in the non-conjugated olefin units contained in the olefin resin is 2 or less. The inclusion of non-conjugated olefin units, which are common units in the copolymer and the olefin resin, and the similar structure of these non-conjugated olefin units, further improves the mechanical strength of the molded article.

[0080] The difference between the number of carbon atoms in the non-conjugated olefin units contained in the copolymer and the number of carbon atoms in the non-conjugated olefin units contained in the olefin resin is more preferably 1 or less, and even more preferably 0. Furthermore, the number of carbon atoms in the olefin units is more preferably 2 to 4, and even more preferably 2 to 3, i.e., polyethylene resins and polypropylene resins are preferred.

[0081] The polyethylene resin refers to a polymer whose main chain contains ethylene units as the main component (for example, more than 50 mol%), and may also contain other units such as propylene units. Furthermore, the polyethylene resin may be thermosetting or thermoplastic. Specifically, examples include polyethylene (homopolymer), ethylene-propylene copolymer (however, with more than 50 mol% ethylene units), etc. There are also types of polyethylene resins such as very low-density polyethylene (VLDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE), and any of these may be used. Among these, from the viewpoint of high versatility, it is preferable to use one or more polyethylene resins selected from the group consisting of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE).

[0082] The aforementioned polypropylene resin refers to a polymer whose main chain contains propylene units as the main component (for example, more than 50 mol%), and may also contain other units such as ethylene units. Furthermore, the polypropylene resin may be thermosetting or thermoplastic. Specifically, examples include polypropylene (homopolymer), ethylene-propylene copolymer (however, with propylene units exceeding 50 mol%), etc.

[0083] From the viewpoint of improving the mechanical strength of the molded article, the olefin resin preferably has a number-average molecular weight (Mn) on a polystyrene basis of 5 to 10,000 kg / mol, more preferably 7 to 1,000 kg / mol, and even more preferably 10 to 1,000 kg / mol.

[0084] From the viewpoint of improving the mechanical strength of the molded article, the olefin resin preferably has a weight-average molecular weight (Mw) on a polystyrene basis of 100 to 300 kg / mol, more preferably 180 to 300 kg / mol, and even more preferably 200 to 280 kg / mol. 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, a GPC such as "HLC-8321GPC / HT" manufactured by Tosoh Corporation can be used.

[0085] -Polystyrene resins and styrene-based thermoplastic elastomers- The styrene-based thermoplastic elastomer has aromatic vinyl polymer blocks (hard segments) and rubber blocks (soft segments), where the aromatic vinyl polymer portion forms physical crosslinks and acts as crosslinking points, while the rubber blocks impart rubber elasticity. The polystyrene resin can be classified according to the arrangement of the soft segments in the molecule, and examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene block copolymer (SIBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and moreover, block copolymers of crystalline polyethylene and ethylene / butylene-styrene random copolymer obtained by hydrogenating a block copolymer of polybutadiene and butadiene-styrene random copolymer, and diblock copolymers of crystalline polyethylene and polystyrene obtained by hydrogenating a block copolymer of polybutadiene or ethylene-butadiene random copolymer and polystyrene. Among these, styrene-isobutylene-styrene block copolymer (SIBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene / propylene-styrene block copolymer (SEPS) are preferred in terms of the balance of mechanical strength, heat stability, weather resistance, chemical resistance, gas barrier properties, flexibility, and processability.

[0086] -Polyvinyl chloride resin- The aforementioned polyvinyl chloride resins are generally classified into the following three types. (Type 1) High molecular weight polyvinyl chloride (PVC) / plasticized polyvinyl chloride (PVC) blend type TPVC This thermoplastic elastomer is composed of a hard segment made of high molecular weight PVC and a soft segment made of PVC plasticized with a plasticizer. The use of high molecular weight PVC in the hard segment provides crosslinking points in the microcrystalline portion. (Type 2) Partially crosslinked PVC / plasticized PVC blend type TPVC This thermoplastic elastomer is made by using PVC with a partially crosslinked or branched structure in the hard segment and PVC plasticized with a plasticizer in the soft segment. (Type 3) PVC / Elastomer Alloy Type TPVC This thermoplastic elastomer is made of PVC for the hard segment and rubber such as partially crosslinked nitrile butadiene rubber (NBR) or TPE such as polyurethane-based TPE or polyester-based TPE for the soft segment. The aforementioned chlorinated polyethylene resin is a flexible resin obtained by reacting polyethylene with chlorine gas in an aqueous suspension or a solvent such as carbon tetrachloride. Crystalline polyethylene blocks are used for the hard segments, and chlorinated polyethylene (CPE) blocks are used for the soft segments. In the CPE blocks, both polyethylene and chlorinated polyethylene components are present as a mixture in a multi-block or random structure.

[0087] -Polyurethane resin- The polyurethane resin is a linear multiblock copolymer consisting of (1) a polyurethane obtained by the reaction of a short-chain glycol and an isocyanate as a hard segment, and (2) a polyurethane obtained by the reaction of a long-chain glycol and an isocyanate as a soft segment. Here, polyurethane is a general term for compounds having a urethane bond (-NHCOO-) obtained by a polyaddition reaction (urethane formation reaction) between an isocyanate (-NCO) and an alcohol (-OH). In the multilayer structure of the present invention, if the elastomer forming the elastomer layer is TPU, stretchability and thermoformability can be improved by laminating the elastomer layer. Furthermore, in such an inner liner, the interlayer adhesion between the elastomer layer and the barrier layer can be improved, resulting in high durability such as crack resistance, and gas barrier properties and stretchability can be maintained even when the inner liner is deformed during use.

[0088] -Polyamide resin- The aforementioned polyamide resin is a multiblock copolymer using polyamide as the hard segment and a low Tg polyether or polyester as the soft segment. The polyamide component constituting the hard segment is selected from nylon 6, 66, 610, 11, 12, etc., with nylon 6 and nylon 12 being the main components. Long-chain polyols such as polyether diols and polyester diols are used as constituent materials for the soft segment. Representative examples of polyether polyols include diol poly(oxytetramethylene) glycol (PTMG) and poly(oxypropylene) glycol, while representative examples of polyester polyols include poly(ethylene adipate) glycol and poly(butylene-1,4 adipate) glycol.

[0089] -Polyester resin- The aforementioned polyester resin is a multiblock copolymer in which polyester is used as the hard segment in the molecule and a polyether or polyester with a low glass transition temperature (Tg) is used as the soft segment.

[0090] -Rubber components- The molded article may contain a rubber component. Here, the conjugated diene-non-conjugated olefin copolymer is excluded from the rubber component. The rubber component provides rubber elasticity to the molded article. Examples of the aforementioned rubber component include natural rubber (NR) and diene rubbers such as synthetic diene rubbers. Specific examples of synthetic diene rubbers include synthetic isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), halogenated butyl rubber, and acrylonitrile-butadiene rubber (NBR). The aforementioned diene rubbers may be used individually or in combination of two or more types. Furthermore, the aforementioned diene rubbers may be modified. The aforementioned rubber component may include a non-diene rubber.

[0091] -Filler- The molded body may contain a filler. By including a filler in the molded body, the mechanical strength of the molded body can be improved. Examples of the aforementioned fillers include carbon black and inorganic fillers. The type of carbon black is not particularly limited and includes, for example, GPF, FEF, HAF, ISAF, SAF, etc., with HAF, ISAF, and SAF being preferred. Examples of the inorganic filler include metal oxides such as silica, alumina, and titania, with silica being preferred among these. There are no particular restrictions on the type of silica, and examples include wet silica (hydrated silica), dry silica (anhydrous silica), and colloidal silica. Furthermore, when silica is included as a filler, the molded body may further contain a silane coupling agent to improve the dispersibility of silica in the molded body. Furthermore, the carbon black and inorganic filler may be resources derived from sources other than petroleum. For example, recycled carbon black obtained by thermal decomposition of used rubber or silica derived from rice husks may be used.

[0092] -Anti-aging agent- The molded article may contain an antioxidant. Examples of antioxidants include amine-ketone compounds, imidazole compounds, amine compounds, phenolic compounds, sulfur compounds, and phosphorus compounds.

[0093] -Softener- The molded article may contain a softening agent. Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, naphthenic oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, and coconut oil; and waxes such as beeswax, carnauba wax, and lanolin. These softening agents may be used individually or in combination of two or more. The softening agent may be derived from resources other than petroleum. For example, recycled oil obtained by thermally decomposing used rubber may be used.

[0094] -Crosslinking agent- The molded article may contain a crosslinking agent. There are no particular restrictions on the crosslinking agent, but common examples include peroxides, sulfur, oximes, amines, and ultraviolet curing agents. Since the copolymer contains conjugated diene units, it can be crosslinked (vulcanized) with sulfur. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.

[0095] -Crosslinking promoter- The molded article may contain a crosslinking accelerator. Examples of crosslinking accelerators (vulcanization accelerators) include guazinine-based, sulfenamide-based, thiuram-based, thiazole-based, aldehydeamine-based, and thiocarbamate-based crosslinking accelerators.

[0096] As described above, the molded article may be produced using the conjugated diene-non-conjugated olefin copolymer as is, or it may be produced by mixing the copolymer with any additional components. Alternatively, the conjugated diene-non-conjugated olefin copolymer may be produced by kneading it alone or together with other optional additives using a kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, roll mixer, or internal mixer. The mixing of each component may be done in one step or in two or more steps. When the molded article is formed from a composition containing the copolymer and other optional additives, the composition may contain, in addition to the copolymer, the above-mentioned olefin resin, rubber component, filler, silane coupling agent, antioxidant, softener, crosslinking agent, crosslinking accelerator, etc. Here, the content of the copolymer in the composition is not particularly limited, but is preferably 50% by mass or more.

[0097] When the components of the composition are melt-kneaded in an extruder and the composition is extruded, the extruded composition may be directly cut into pellets, or strands may be formed and then the strands cut into pellets in a pelletizer. The shape of the pellets can be general shapes such as cylinders, prismatics, and spheres.

[0098] The molded article may be manufactured by melting and kneading the composition and then extruding it, or by hot pressing the composition. The hot pressing temperature is preferably 120 to 160°C, and more preferably 130 to 150°C.

[0099] <Method for hydrophilizing molded bodies> The present invention provides a method for hydrophilizing the surface of a molded article comprising a conjugated diene-non-conjugated olefin copolymer having conjugated diene units and non-conjugated olefin units, This process is characterized by including an oxidation step for the molded body. By going through the process described above, good hydrophilicity can be imparted to the surface of the molded product.

[0100] Furthermore, the oxidation of the molded body is not particularly limited as long as it can increase the reactivity of the surface of the molded body. For example, oxidation can be carried out using air, but it is preferable to carry out the following steps (i) or (ii) in order to ensure more reliable oxidation of the surface. (i) A step of bringing the molded body into contact with chlorine dioxide gas and then irradiating the surface of the molded body with light. (ii) A step of bringing the molded body into contact with a gas obtained by irradiating chlorine dioxide gas with light.

[0101] Here, the light irradiation is not particularly limited as long as it can make the surface of the molded body hydrophilic. Examples include UV irradiation, LED irradiation, and combinations thereof. Among these, the light irradiation is preferably a combination of UV irradiation and LED irradiation (LED-UV light irradiation).

[0102] By irradiating the surface of the molded body with LED-UV light, the oxidation rate of the surface of the molded body can be increased. The conditions for the LED-UV light irradiation are not particularly limited. For example, the temperature should be above room temperature, the irradiation time should be 10 seconds to 120 minutes, and the irradiation intensity should be 1 to 100 mW / cm².2 It can be done this way.

[0103] The structure of the molded article and the structure of the conjugated diene-non-conjugated olefin copolymer are the same as those described above for the molded article of the present invention.

[0104] <complex> Next, the composite of the present invention will be described. The composite of the present invention is characterized by comprising the molded article of the present invention described above and a metal. By using the aforementioned molded body as a composite with a metal, it is possible to improve the adhesion between the metal and the molded body while maintaining excellent tensile strength.

[0105] Examples of the composite of the present invention include a configuration in which a cord made of the metal is covered using the molded body of the present invention described above, and a configuration in which a molded body with a coating film is formed on a plate-shaped metal. The method for covering the aforementioned metal cords with the molded body of the present invention is not particularly limited, but for example, a method can be used in which predetermined brass-plated metal cords are arranged in parallel at predetermined intervals, these metal cords are coated from both the top and bottom with a sheet-like molded body about 0.5 mm thick, and then heat-treated at a temperature of about 160°C for about 20 minutes. Furthermore, as a method for forming a molded body with a coating on a plate-shaped metal, one method involves applying a composition to be used as the material for the molded body to a predetermined thickness onto a predetermined plated metal plate, and then heat-curing the composition.

[0106] The metal cord may be either a monofilament or a multifilament (twisted cord or bundled cord), and its shape is not limited. There are no particular restrictions on the twisting structure when the metal cord is a twisted cord, and examples of twisting structures include single twist, double twist, layer twist, and composite twist of double twist and layer twist. Examples of these metal cords include cords made of metals such as steel, iron, and copper, and it is preferable that the surface is treated with plating, adhesive treatment, etc., from the viewpoint of ensuring suitable adhesion with the rubber composition. The surface of the filament may be plated. Examples of plating types include zinc (Zn) plating, copper (Cu) plating, tin (Sn) plating, brass (copper-zinc (Cu-Zn)) plating, bronze (copper-tin (Cu-Sn)) plating, and ternary plating containing copper, zinc, and cobalt. Among these, brass plating and ternary plating containing copper, zinc, and cobalt are preferred.

[0107] <Applications of molded products> The molded articles of the present invention have excellent durability, shape recovery, and self-healing properties, and can therefore be used in products for various applications, such as rubber products and resin products. More specifically, the molded articles of this embodiment are suitable for tires and automobile parts (automobile seats, automobile batteries (lithium-ion batteries, etc.), weatherstrips, hose tubes, cables, sealing materials, etc.), ship parts, building materials, etc. Other applications of the molded bodies of this embodiment include crawlers, hoses, resin piping, sound-absorbing materials, bedding, precision parts for office equipment (OA rollers), bicycle frames, golf balls, tennis rackets, golf shafts, resin additives, filters, adhesives, sealants, inks, medical devices (medical tubes, bags, microneedles, rubber sleeves, artificial organs, caps, gaskets, syringe gaskets, drug stoppers, prosthetics, artificial limbs), cosmetics (UV powder, puffs, containers, wax, shampoo, conditioner), detergents, and building materials (flooring materials, vibration damping rubber, seismic isolation rubber, building films). It is suitable for use in sound-absorbing materials, waterproof sheets, heat-insulating materials, joint fillers, sealants, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, electronic devices, communication equipment, aircraft parts, machine parts, electronic components, agricultural materials, electric wires, cables, textiles (wearable substrates), daily necessities (toothbrushes, shoe soles, eyeglasses, lures, binoculars, toys, dust masks, garden hoses), robot parts, optical components, road materials (asphalt, guardrails, poles, signs), protective equipment (shoes, puncture-resistant safety shoes, bulletproof vests), electrical equipment exterior parts, OA exterior parts, soles, sealants, etc. In the above, OA stands for office automation, UV for ultraviolet, and EL for electro-luminescence.

[0108] <Rubber Products> The rubber product of the present invention is characterized by using the molded body of the present invention as described above. In other words, the rubber product according to this embodiment comprises the molded body described above. Because the rubber product uses the molded body described above, it has excellent durability, shape recovery, and self-healing properties, and furthermore, it has excellent tensile strength while also having good adhesion between the metal member and the molded body portion. Suitable examples of the aforementioned rubber products include those listed in the section on (Applications of molded products). For example, they can be used in tire components, automotive parts (automotive seats, hoses and tubes, vibration-damping rubber, cables, sealing materials, etc.), rubber tracks, hoses, adhesives, sealants, inks, medical devices, building materials, packaging materials, daily necessities, etc. Among these, the rubber product of the present invention is preferably a tire, rubber track, or hose, as this allows for greater enjoyment of the effects of the present invention.

[0109] <Resin products> The resin product of the present invention is characterized by using the molded body of the present invention as described above. In other words, the resin product according to this embodiment comprises the molded body described above. Because the resin product uses the molded body described above, it has excellent durability, shape recovery, and self-healing properties, and furthermore, it has excellent tensile strength while also having good adhesion between the metal member and the molded body portion. Suitable resin products include, for example, those listed in the section on (Applications of molded articles). [Examples]

[0110] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples.

[0111] [Preparation of each sample] Molded bodies of each sample were prepared and evaluated according to the following conditions.

[0112] (1) Synthesis of copolymers having conjugated diene units and non-conjugated olefin units (Synthesis of copolymer A) 75g of styrene and 675g of toluene were added to a thoroughly dried 2000mL pressure-resistant stainless steel reactor. Meanwhile, in a glove box under a nitrogen atmosphere, 0.075 mmol of ((1-benzyldimethylsilyl-3-methyl)indenyl)bis(bis(dimethylsilyl)amide)gadolinium complex {(1-BnMe2Si-3-Me]C9H5Gd[N(SiHMe2)2]2}, 0.083 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate [Me2NHPhB(C6F5)4], and 0.35 mmol of diisobutylaluminum hydride were added to a glass container, and then 30 g of toluene was added to prepare the catalyst solution. The resulting catalyst solution was added to the pressure-resistant stainless steel reactor and heated to 60°C. Next, ethylene was added to the pressure-resistant stainless steel reactor at a pressure of 1.5 MPa, and copolymerization was carried out at 75°C for a total of 3 hours. During copolymerization, 80 g of toluene solution containing 20 g of 1,3-butadiene was continuously added at a rate of 0.4 to 0.6 mL / min. Next, 1 mL of a 5% by mass isopropanol solution of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol)(NS-5) was added to the pressure-resistant stainless steel reactor to stop the reaction. Next, the copolymer was separated using a large amount of methanol and vacuum-dried at 50°C to obtain copolymer A.

[0113] (Synthesis of copolymer B) In a thoroughly dried 2000 mL pressure-resistant stainless steel reactor, 30 g of styrene, 20 g of toluene solution containing 5 g of 1,3-butadiene, and 430 g of toluene were added. Meanwhile, in a glove box under a nitrogen atmosphere, 0.075 mmol of mono(1,3-bis(tert-butyldimethylsilyl)indenyl)bis(bis(dimethylsilyl)amide)gadolinium complex {1,3-[(t-Bu)Me2Si]2C9H5Gd[N(SiHMe2)2]2}, 0.075 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate [Me2NHPhB(C6F5)4], and 0.35 mmol of diisobutylaluminum hydride were added to a glass container, and then 20 mL of toluene was added to prepare the catalyst solution. The resulting catalyst solution was added to the pressure-resistant stainless steel reactor and heated to 60°C. Next, ethylene was added to the pressure-resistant stainless steel reactor at a pressure of 1.0 MPa, and copolymerization was carried out at 75°C for a total of 3 hours. During copolymerization, 120 g of a toluene solution containing 30 g of 1,3-butadiene was continuously added at a rate of 2.5 to 2.8 mL / min. Next, 1 mL of a 5% by mass isopropanol solution of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol)(NS-5) was added to the pressure-resistant stainless steel reactor to stop the reaction. Next, the copolymer was separated using a large amount of methanol and vacuum-dried at 50°C to obtain copolymer B.

[0114] (Synthesis of copolymer C) In a thoroughly dried 2000 mL pressure-resistant stainless steel reactor, 30 g of styrene, 20 g of toluene solution containing 5 g of 1,3-butadiene, and 430 g of toluene were added. Meanwhile, in a glove box under a nitrogen atmosphere, 0.075 mmol of mono(1,3-bis(tert-butyldimethylsilyl)indenyl)bis(bis(dimethylsilyl)amide)gadolinium complex {1,3-[(t-Bu)Me2Si]2C9H5Gd[N(SiHMe2)2]2}, 0.075 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate [Me2NHPhB(C6F5)4], and 0.35 mmol of diisobutylaluminum hydride were added to a glass container, and then 20 mL of toluene was added to prepare the catalyst solution. The resulting catalyst solution was added to the pressure-resistant stainless steel reactor and heated to 60°C. Next, ethylene was added to the pressure-resistant stainless steel reactor at a pressure of 1.0 MPa, and copolymerization was carried out at 75°C for a total of 3 hours. During copolymerization, 240 g of a toluene solution containing 60 g of 1,3-butadiene was continuously added at a rate of 2.5 to 2.8 mL / min. Next, 1 mL of a 5% by mass isopropanol solution of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol)(NS-5) was added to the pressure-resistant stainless steel reactor to stop the reaction. Next, the copolymer was separated using a large amount of methanol and vacuum-dried at 50°C to obtain copolymer C.

[0115] (2) Physical properties of copolymers having conjugated diene units and non-conjugated olefin units The following physical properties were measured for copolymers A to D obtained as described above. The results are shown in Table 1. (2-1) Number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, Column: Tosoh GMH] HR Using two H(S)HT tubes and a differential refractometer (RI) as the detector, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymer were determined relative to monodisperse polystyrene. The measurement temperature was 40°C.

[0116] (2-2) Content of butadiene units, ethylene units, and styrene units The content (mol%) of ethylene units, butadiene units, and styrene units in the copolymer is as follows: 1 The integral ratio of each peak in the 1H-NMR spectrum (100°C, d-tetrachloroethane standard: 6 ppm) was determined.

[0117] (2-3) Melting point (Tm) The melting point (Tm) of the copolymer was measured using a differential scanning calorimeter (DSC, manufactured by T.A. Instruments Japan, "DSCQ2000") in accordance with JIS K 7121-1987.

[0118] (2-4) Tensile strength (Tb) and elongation at break (Eb) The specimens were molded into a dumbbell-shaped No. 3 form according to JIS K 6251 (2017) and used as test pieces. Tensile strength (Tb) was measured according to JIS K 6251 (2017) using a tensile testing apparatus (manufactured by Instron), by elongating the test specimen to 100% at 25°C and measuring the maximum tensile force required to break the specimen. The elongation at break (Eb) was determined by stretching the specimen at a speed of 100 mm / min at 25°C, measuring the length at which the specimen broke, and calculating the length relative to the length before stretching (100%).

[0119] (2-5) Confirmation of the acyclic structure of the main chain 13 The absence of peaks in the 10-24 ppm range in the 1C-NMR spectrum chart confirmed that the main chain consists solely of acyclic structures.

[0120] [Table 1]

[0121] (3) Oxidation treatment with chlorine dioxide gas and irradiation with LED-UV light Copolymers A to C and low-density polyethylene (LLDPE, Yumerit 1540F manufactured by Ube Maruzen Polyethylene) were prepared as test specimens measuring 4 cm × 11 cm × 200 μm to 2.0 mm, and then subjected to oxidation treatment and LED-UV light irradiation under the following conditions. Sodium chlorite (NaClO2) (200 mg) was dissolved in 20 mL of ultrapure water, and then 37% by mass HCl aqueous solution (100 μL) was added to prepare a 1% by mass hydrochloric acid-acidified NaClO2 aqueous solution (radical generation reaction system). Subsequently, as shown in Figures 1(a) and (b), the hydrochloric acid-acidified NaClO2 aqueous solution was added to the outer container of a 10 cm × 10 cm double-walled glass container (Petri dish). Meanwhile, the treatment sample was placed in the inner container of the double-walled glass container. Furthermore, the double-walled glass container was covered with a lid to prevent leakage of internal gas. Subsequently, under the temperature set using a heating device, the hydrochloric acid-acidified NaClO2 aqueous solution in the glass double-walled container was irradiated with LED-UV light with a wavelength of 365 nm from above the glass double-walled container under the following conditions. Reaction temperature: 30°C ·LED-UV light irradiation: 20mW / cm 2 (λ=365nm) • Reaction time: 0 seconds, 90 seconds The test specimens were then washed with water and dried under reduced pressure for 24 hours to obtain the target product (oxidation-treated sample).

[0122] (4) Catalytic oxidation treatment Copolymer C was subjected to oxidation treatment under the following conditions. After dissolving 1 g of copolymer C in 100 mL of toluene, 25 mg of cobalt(II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and the mixture was heated to 80°C. Then, oxygenated air was bubbled through the mixture for 30 minutes while stirring, and the mixture was cooled to room temperature. Isopropanol was added to precipitate the polymer. The polymer separated by filtration was dried under reduced pressure to obtain copolymer C oxidized by catalytic oxidation. The obtained oxidized copolymer C was compared with the sample oxidized with chlorine dioxide gas as described above in terms of weight-average molecular weight, number-average molecular weight, and molecular weight distribution. The results of the comparison are shown in Table 2. [Table 2]

[0123] The comparison revealed that both the weight-average molecular weight and the number-average molecular weight decreased in the catalytic oxidation method compared to before oxidation, and that the molecular weight distribution was further broadened. From this, it became clear that the oxidation method using chlorine dioxide gas is preferable in terms of maintaining the molecular weight and molecular weight distribution of the original copolymer.

[0124] [evaluation] The following evaluations were performed on each of the obtained polymers A-C and low-density polyethylene samples. (1) Contact angle measurement For copolymers A-C and low-density polyethylene (LLDPE, Ube Maruzen Polyethylene's Yumerit 1540F), the contact angle was measured after oxidation treatment and LED-UV light irradiation. Specifically, under conditions of 25°C and 55% RH, a 1.0 μL drop of water was placed on a flat sample, left for 10 seconds, and then the contact angle (°) was measured using a contact angle meter [Drop Master DM300, manufactured by Kyowa Interface Science Co., Ltd.]. The measurement results are shown in Table 3.

[0125] (2) Measurement of tensile strength Tensile strength measurements were performed on copolymers A and B, and low-density polyethylene (LLDPE, Yumerit 1540F manufactured by Ube Maruzen Polyethylene) after oxidation treatment and LED-UV light irradiation. Specifically, tensile strength was measured using a sample with a thickness of 200 μm. The measurement results are shown in Table 3.

[0126] (3) Staining test The dyeability of copolymers A to C and low-density polyethylene (LLDPE, Yumerit 1540F manufactured by Ube Maruzen Polyethylene) was evaluated after oxidation treatment and LED-UV light irradiation. Specifically, the oxidized sample was immersed in 50 mL of toluidine blue aqueous solution (1 mM NaOH, 0.1% TBO (Sigma-Aldrich, Germany)) and stirred at room temperature for 30 minutes. After the predetermined time, the sample plate was removed and washed with NaOH aqueous solution (1 mM) to remove excess toluidine blue. The degree of staining was evaluated visually according to the following criteria, and the results are shown in Table 3. ◎: Stained noticeably blue ○: Dyed blue △: Trace staining ×: Almost no staining

[0127] (4) Metal adhesion test Copolymers A, B, and C, as well as low-density polyethylene (LLDPE, Yumerit 1540F manufactured by Ube Maruzen Polyethylene), were evaluated for their metal adhesion after oxidation treatment and LED-UV light irradiation. Specifically, a test specimen was prepared by overlapping a 1cm x 5cm aluminum plate with a thickness of 1mm and a 1cm x 5cm sample with a thickness of 2mm in a 1cm x 1cm area, and then heating them at 110°C. The degree of adhesion was evaluated by 180° tensile shear and torsional shear. The evaluation was carried out according to the following criteria, and the results are shown in Table 3. ○: It doesn't come off with tension and shear, but twists, bends the aluminum, and then peels off. △: Does not come off with tension or shear, but peels off when twisted. ×: Detaches under tensile shear.

[0128] [Table 3]

[0129] The results in Table 3 show that the samples following the present invention (polymers A to C that underwent oxidation treatment and LED-UV light irradiation) exhibited a smaller contact angle and superior dyeability and metal adhesion. Furthermore, no significant decrease in tensile strength was observed. [Industrial applicability]

[0130] According to the present invention, it is possible to provide molded articles, composites, resin products, and rubber products that achieve both excellent tensile strength and hydrophilicity. Furthermore, according to the present invention, it is possible to provide a method for hydrophilizing a molded article that has excellent tensile strength while also improving its hydrophilicity.

Claims

1. A molded article comprising a conjugated diene-non-conjugated olefin copolymer having conjugated diene units and non-conjugated olefin units, A molded body characterized in that the contact angle between the surface of the molded body and water is 90° or less.

2. The molded article according to claim 1, characterized in that the conjugated diene-non-conjugated olefin copolymer has a melting point of 50 to 120°C.

3. The molded article according to claim 1, characterized in that the conjugated diene-non-conjugated olefin copolymer has a content of conjugated diene units that is greater than 0 mol% and less than or equal to 50 mol%, and a content of non-conjugated olefin units that is 50 mol% or more and less than 100 mol%.

4. The molded article according to claim 1, characterized in that the copolymer further comprises aromatic vinyl units.

5. Furthermore, the molded article according to claim 1, characterized in that it contains a resin component.

6. Furthermore, the molded article according to claim 5, characterized in that the resin component is at least one selected from the group consisting of olefin resins, polystyrene resins, and polyvinyl chloride resins.

7. The molded article according to claim 1, characterized in that the film thickness of the molded article is 10 μm to 2.0 mm.

8. The molded body according to claim 1, characterized in that the surface of the molded body is hydrophilic.

9. A method for hydrophilizing the surface of a molded article containing a conjugated diene-non-conjugated olefin copolymer having conjugated diene units and non-conjugated olefin units, A method for hydrophilizing a molded article, characterized by including an oxidation step for the molded article.

10. The method for hydrophilizing a molded body according to claim 9, characterized in that the oxidation of the molded body includes the step of bringing the molded body into contact with chlorine dioxide gas and then irradiating the surface of the molded body with light.

11. The method for hydrophilizing a molded body according to claim 9, characterized in that the oxidation of the molded body includes a step of bringing the molded body into contact with a gas obtained by irradiating chlorine dioxide gas with light.

12. A composite comprising a molded body according to any one of claims 1 to 8 and a metal.

13. The composite according to claim 11, characterized in that the metal is in the form of a cord or a plate.

14. A rubber product using a molded body according to any one of claims 1 to 8, characterized in that the rubber product is a tire, a rubber crawler, or a hose.

15. A resin product characterized by using a molded article according to any one of claims 1 to 8.

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