Hydrogenated block copolymers, gel compositions, cable fillers, cables, cosmetics, lubricants, and greases

Abstract

This hydrogenated block copolymer (a) is a hydrogenated product of a block copolymer that has one polymeric block (A) in which a main body thereof is an aromatic vinyl compound unit, and at least one polymeric block (B) in which main bodies thereof are a butadiene unit (Bd) and an isoprene unit (Ip). The hydrogenated block copolymer satisfies the following requirements (I) and (II). (I) The formula (i) is satisfied.　(i): α×β>6.500×109 (In formula (i), α represents the weight average molecular weight of the polymeric block (A), and β represents the weight average molecular weight of the hydrogenated block copolymer (a).) (II) The level of vinylation of the polymeric block (B) is less than 35%.

Description

[Technical Field]

[0001] The present invention relates to a hydrogenated block copolymer, a gel composition, a cable filler, a cable, a cosmetic, a lubricating oil, and a grease, and in particular to a hydrogenated block copolymer, a gel composition containing the hydrogenated block copolymer, a cable filler containing the gel composition, a cable containing the gel composition, a cosmetic containing the gel composition, a lubricating oil containing the gel composition, and a grease containing the gel composition. [Background technology]

[0002] Hydrogenated block copolymers are used in various applications (cable fillers, cosmetics, lubricating oils, greases, etc.) as gel compositions in combination with oils. Cables such as optical fiber cables and electric cables are generally installed with one or more cables housed in a resin protective tube or the like. Therefore, if an impact or stress is applied to the protective tube during installation, there is a problem that the protective tube and the internal cable, or the internal cables, may interfere with each other, resulting in damage to the internal cable. One method for solving this problem is, for example, to fill the gap between the protective tube and the cable with a cable filler such as a gel composition. In the case of optical fiber cables, another method is to fill a cable filler such as a gel composition around the optical fiber core wire within the cable to prevent damage to the delicate optical fiber core wire. Such cable fillers must be elastic enough to protect the interior, yet have a viscosity that allows them to be easily filled into protective tubes and cables and prevents the filler from flowing out if the protective tubes or cables are damaged. They are also required to exhibit consistent properties at various temperatures and to prevent water from penetrating into the protective tubes or cables if they are damaged. For example, Patent Document 1 describes a filler material containing a specific oil, a styrene-(ethylene / propylene) diblock copolymer, a photoantioxidant, and a photometal deactivator. Patent Document 2 also describes a cable filler composition for optical fiber cables, which contains (i) a Fischer-Tropsch derived base oil; and (ii) a thickening system, the thickening system containing at least one block copolymer. Generally, cosmetics with cleansing effects include soap, cleansing cream, cleansing foam, cleansing oil, cleansing lotion, etc. Among these, cleansing oil is a composition in which various additives such as thickeners and moisturizers are added to oil, which has high cleansing ability for oil-based cosmetics. Thickeners used industrially for cleansing oil include water-soluble resins such as gum arabic, clay minerals such as hectorite, and lipophilic polymer compounds such as olefin copolymers. For example, Patent Document 3 describes a cleansing composition containing oil, a styrene / olefin block copolymer, and a nonionic surfactant. Furthermore, lubricating oils used as engine oils and automatic transmission fluids contain additives commonly called viscosity index improvers to improve their viscosity characteristics. Examples of these viscosity index improvers include olefin copolymers, polymethacrylates, and styrene / hydrogenated diene block copolymers. For example, Patent Document 4 describes a lubricating oil containing a styrene / hydrogenated isoprene block copolymer as a viscosity index improver. Grease is also used in sliding members of automobiles and various industrial machines to reduce friction on their sliding surfaces. Grease is particularly suitable for use in sliding locations where it is difficult to apply lubricating oil. Examples of grease thickeners include olefin copolymers, polymethacrylates, and styrene / hydrogenated diene block copolymers. For example, Patent Document 5 describes a grease containing a styrene / hydrogenated isoprene block copolymer as a thickener. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-67913 [Patent Document 2] Special Publication No. 2015-527448 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-100985 [Patent Document 4] Special Publication No. 2006-521450 [Patent Document 5] Japanese Patent Application Laid-Open No. 2016-141763 Summary of the Invention [Problem to be solved by the invention]

[0004] The filler compositions described in Patent Documents 1 and 2 have a viscosity suitable for use as a cable filler, can prevent water from penetrating into a protective tube, and have low temperature dependency, but further improvements in performance (for example, further improvements in dropping point) are desired. Furthermore, from an economical standpoint, thickeners contained in cosmetics are desired that have a high thickening effect, i.e., thickeners that require a small amount of addition to achieve the desired viscosity of the cosmetics. Similarly, from a similar standpoint, viscosity index improvers contained in lubricating oils are desired that require a small amount of addition to achieve the desired viscosity of the lubricating oil. Similarly, from a similar standpoint, thickeners contained in greases are desired that require a small amount of addition to achieve the desired consistency of the grease.

[0005] Therefore, an object of the present invention is to provide a hydrogenated block copolymer that can solve the above-mentioned problems when used in combination with an oil (base oil), a gel composition containing the hydrogenated block copolymer, a cable filler containing the gel composition, a cable containing the gel composition, a cosmetic containing the gel composition, a lubricating oil containing the gel composition, and a grease containing the gel composition. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found a hydrogenated block copolymer having one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip), wherein the product of the weight-average molecular weight α of the polymer block (A) and the weight-average molecular weight β of the hydrogenated block copolymer (a) is 6.500 × 10 9 Super(α×β>6.500×10 9 ) and by using a hydrogenated block copolymer in which the degree of vinylation of the polymer block (B) is less than 35%, the above-mentioned problems can be solved, and the present invention has been completed based on this finding. That is, the present invention is as follows.

[0007] [1] A hydrogenated block copolymer (a) which is a hydrogenated product of a block copolymer having one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip), and which satisfies the following requirements (I) and (II): (I) The following formula (i) is satisfied: α×β>6.500×10 9 (i) (In formula (i), α represents the weight average molecular weight of the polymer block (A), and β represents the weight average molecular weight of the hydrogenated block copolymer (a).) (II) The degree of vinylation of the polymer block (B) is less than 35%. [2] The hydrogenated block copolymer according to [1] above, wherein the content of the polymer block (A) in the hydrogenated block copolymer (a) is 40 mass % or less. [3] The hydrogenated block copolymer according to [1] or [2], wherein the polymer block (B) has a molar ratio of butadiene units (Bd) to isoprene units (Ip) of Bd:Ip=25:75 to 75:25. [4] The hydrogenated block copolymer according to any one of [1] to [3], wherein the hydrogenated block copolymer (a) is a hydrogenated product of a diblock copolymer having one polymer block (A) and one polymer block (B). [5] The hydrogenated block copolymer according to any one of the above [1] to [4], wherein the hydrogenation rate of the polymer block (B) is 90.0 mol % or more. [6] A gel composition comprising the hydrogenated block copolymer (a) according to any one of [1] to [5] above and a base oil (b). [7] The gel composition according to [6] above, wherein the viscosity index of the base oil (b) is 70 to 150. [8] A cable filler comprising the gel composition according to [6] or [7]. [9] A cable containing the gel composition described in [6] or [7].

[10] The cable described in [9], wherein the cable is an optical fiber cable.

[11] A cosmetic comprising the gel composition described in [6] or [7].

[12] A lubricating oil containing the gel composition according to [6] or [7].

[13] A grease containing the gel composition described in [6] or [7]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a hydrogenated block copolymer that can solve the above-mentioned problems when used in combination with an oil (base oil), a gel composition containing the hydrogenated block copolymer, a cable filler containing the gel composition, a cable containing the gel composition, a cosmetic containing the gel composition, a lubricating oil containing the gel composition, and a grease containing the gel composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. In this specification, the preferred definitions can be adopted arbitrarily, and it can be said that a combination of preferred definitions is more preferred. In addition, in this specification, the expression "XX to YY" means "XX or more and YY or less." Furthermore, in this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, in this specification, the term "unit of ~" (where "~" indicates a monomer) means "a structural unit derived from ~", for example, "aromatic vinyl compound unit" means "a structural unit derived from an aromatic vinyl compound".

[0010] The hydrogenated block copolymer (a) of the present invention has one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip), and satisfies the following requirements (I) and (II): (I) The following formula (i) is satisfied: α×β>6.500×10 9 (i) (In formula (i), α represents the weight average molecular weight of the polymer block (A), and β represents the weight average molecular weight of the hydrogenated block copolymer (a).) (II) The degree of vinylation of the polymer block (B) is less than 35%. The present inventors have found that in a hydrogenated block copolymer that satisfies the above formula (i) and has one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip), by setting the degrees of vinylation of α×β and polymer block (B) within the above ranges, the copolymer exhibits the ability to retain its shape up to higher temperatures when used in combination with oil, and further, that this function can be exerted even in a smaller amount.

[0011] [Hydrogenated block copolymer (a)] The hydrogenated block copolymer (a) is a hydrogenated product of a block copolymer having at least one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip). Furthermore, the hydrogenated block copolymer (a) satisfies the following requirements (I) and (II). (I) The following formula (i) is satisfied: α×β>6.500×10 9 (i) (In formula (i), α represents the weight average molecular weight of the polymer block (A), and β represents the weight average molecular weight of the hydrogenated block copolymer (a).) (II) The degree of vinylation of the polymer block (B) is less than 35%.

[0012] α×β is 6.500×10 9 There is no particular limitation as long as it is greater than 6,600 × 10 9 ~3.000×10 10 , more preferably 6.700 × 10 9 ~2.000×10 10 , and even more preferably 6,800×10 9 ~1.200×1010 , particularly preferably 8,000 × 10 9 ~1.000×10 10 Within the above range, when a gel composition is prepared by combining it with oil, the degree of vinylation can be adjusted to fall within a specific range, as will be described later, to exhibit properties such as a dropping point and a thickening effect. The polymer block (A) and the polymer block (B) will be described below in order.

[0013] <Polymer block (A)> The polymer block (A) is mainly composed of aromatic vinyl compound units. Here, "mainly composed" means that the polymer block (A) contains 50% by mass or more of aromatic vinyl compound units based on the total mass of the polymer block (A). From the viewpoint of improving the dropping point of the gel composition, the content of aromatic vinyl compound units in the polymer block (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may even be 100% by mass, based on the total mass of the polymer block (A). The aromatic vinyl compound is not particularly limited, and examples thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro- ...α-chloro-o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, α-chloro-o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, α-chloro-o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, Examples of suitable styrene include styrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, and vinylnaphthalene. Among these, from the viewpoint of the balance between production cost and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0014] The polymer block (A) may contain structural units derived from monomers other than aromatic vinyl compounds, such as monomers constituting the polymer block (B) described below. However, the content of structural units derived from aromatic vinyl compounds in the polymer block (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.

[0015] The weight average molecular weight (Mw) of the polymer block (A) is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, even more preferably 30,000 to 59,000, still more preferably 31,000 to 55,000, and particularly preferably 34,000 to 50,000, from the viewpoint of improving the dropping point and increasing the viscosity of the gel composition.

[0016] The "weight average molecular weight" of polymer block (A) described herein is the weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). In the production of hydrogenated block copolymer (a), when an aromatic vinyl compound is first polymerized to form polymer block (A) and then butadiene and isoprene are polymerized to form polymer block (B), the weight average molecular weight can be determined by collecting a portion of the reaction solution after the formation of polymer block (A) and measuring it by GPC. In the production of hydrogenated block copolymer (a), when butadiene and isoprene are first polymerized to form polymer block (B) and then an aromatic vinyl compound is polymerized to form polymer block (A), the weight average molecular weight can be determined by subtracting the weight average molecular weight (Mw) of polymer block (B) from the weight average molecular weight (Mw) of the resulting block copolymer (before hydrogenation). In this case, the weight average molecular weight of polymer block (B) can be determined by collecting a portion of the reaction solution after the formation of polymer block (B) and measuring it by GPC. More specifically, the value is measured according to the method described in the Examples.

[0017] From the viewpoint of the hardness (consistency) and viscosity of the resulting gel composition, the content of polymer block (A) in hydrogenated block copolymer (a) is preferably 40% by mass or less, more preferably 15 to 40% by mass, even more preferably 25 to 39% by mass, even more preferably 28 to 38% by mass, and particularly preferably 29 to 33% by mass. Furthermore, from the viewpoint of the mechanical properties of the resulting gel composition, it is preferable that the hydrogenated block copolymer (a) of the present invention contains structural units derived from an aromatic vinyl compound only in polymer block (A). For example, when only polymer block (A) contains structural units derived from styrene, the content of polymer block (A) in hydrogenated block copolymer (a) indicates the styrene content.

[0018] In the present invention, the filler is required to have a low viscosity under high shear rate conditions so that it can be easily filled into protective tubes and cables. On the other hand, the filler is required to have a high viscosity under low shear rate conditions so that it is less likely to leak out of the cable under low shear rate conditions so that it will leak out if the cable is damaged during use. Therefore, it is preferable that the ratio of the viscosity under low shear rate conditions to the viscosity under high shear rate conditions is high. To achieve a high viscosity ratio, the content of polymer block (A) in the hydrogenated block copolymer (a) is preferably 28 to 40% by mass, more preferably 30 to 37% by mass.

[0019] The content of the polymer block (A) in the hydrogenated block copolymer (a) is 1 The values ​​are determined by H-NMR spectroscopy, and more specifically, the values ​​are measured according to the method described in the Examples. When the content of the polymer block (A) is about 26% by mass or more, the viscosity under high shear rate conditions can be kept low, making it easier to fill the gel composition into a protective tube or cable during cable production. This improves the production efficiency of optical fiber cables, etc. From this viewpoint, the content of the polymer block (A) is preferably 28 to 40% by mass, more preferably 30 to 37% by mass.

[0020] <Polymer block (B)> The polymer block (B) is primarily composed of butadiene units (Bd) and isoprene units (Ip). Here, "primarily composed" means that the polymer block (B) contains butadiene units (Bd) and isoprene units (Ip), and that the total amount of butadiene units (Bd) and isoprene units (Ip) is 50% by mass or more, based on the total mass of the polymer block (B). The total content of butadiene units (Bd) and isoprene units (Ip) in the polymer block (B) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the polymer block (B), with the upper limit being 100% by mass. When the total content of butadiene units (Bd) and isoprene units (Ip) in the polymer block (B) is within the above range, the solubility of the hydrogenated block copolymer (a) in the base oil (b) is increased, facilitating the production of a gel composition. The polymer block (B) mainly comprises butadiene units (Bd) and isoprene units (Ip), and may further contain structural units derived from at least one selected from, for example, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. The content ratio (Bd / Ip) of butadiene units (Bd) and isoprene units (Ip) (molar ratio) is not particularly limited, but from the viewpoint of improving performance, it is preferably 25 / 75 to 75 / 25, more preferably 40 / 60 to 60 / 40. The bonding form of the butadiene units (Bd) and isoprene units (Ip) in the polymer block (B) is not particularly limited, and may be any of random, tapered, alternating, multiblock, block, and combinations of two or more of these.

[0021] The bond configuration of butadiene and isoprene constituting polymer block (B) is not particularly limited. For example, butadiene may have a 1,2-bond or a 1,4-bond, and isoprene may have a 1,2-bond, a 3,4-bond, or a 1,4-bond. In this specification, the amount of 1,2-bonds in the butadiene units of the polymer block (B) is referred to as the amount of vinyl bonds, and the total amount of 1,2-bonds and 3,4-bonds in the isoprene units of the polymer block (B) is referred to as the amount of vinyl bonds, and the content of vinyl bonds in all bonding forms of the polymer block (B) is referred to as the degree of vinylation (%). As in the examples, the amount of 1,2-bonds and the amount of 3,4-bonds are 1 It can be calculated by H-NMR measurement.

[0022] The degree of vinylation of the polymer block (B) is not particularly limited as long as it is less than 35%, and is preferably 20% or less, more preferably 2 to 15%, even more preferably 5 to 10%, and particularly preferably 5 to 7%. 9 The dropping point of the gel composition can be increased by using a hydrogenated block copolymer having one polymer block (A) mainly composed of aromatic vinyl compound units and at least one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip) and by setting the degree of vinylation of polymer block (B) of the hydrogenated block copolymer within the above-mentioned range.

[0023] The weight average molecular weight (Mw) of the polymer block (B) is preferably 50,000 to 600,000, more preferably 80,000 to 300,000, and particularly preferably 100,000 to 200,000, from the viewpoint of improving the dropping point and increasing the viscosity of the gel composition. The "weight average molecular weight" of polymer block (B) is the weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC), as described above. When producing hydrogenated block copolymer (a), an aromatic vinyl compound is first polymerized to form polymer block (A), and then butadiene and isoprene are polymerized to form polymer block (B), the weight average molecular weight (Mw) can be determined by subtracting the weight average molecular weight (Mw) of polymer block (A) from the weight average molecular weight (Mw) of the resulting block copolymer (before hydrogenation). In this case, the weight average molecular weight (Mw) of polymer block (A) can be determined by collecting a portion of the reaction solution after forming polymer block (A) and subjecting it to GPC measurement. When producing hydrogenated block copolymer (a), butadiene and isoprene are first polymerized to form polymer block (B), and then an aromatic vinyl compound is polymerized to form polymer block (A), the weight average molecular weight (Mw) can be determined by collecting a portion of the reaction solution after forming polymer block (B) and subjecting it to GPC measurement. More specifically, the values ​​are measured according to the methods described in the Examples.

[0024] Furthermore, from the viewpoint of heat resistance and weather resistance, the carbon-carbon double bonds of the polymer block (B) in the hydrogenated block copolymer (a) are preferably hydrogenated (hereinafter sometimes abbreviated as "hydrogenation"). The hydrogenation rate (hydrogenation ratio) of the polymer block (B) in the hydrogenated block copolymer (a) is not particularly limited, but is preferably 90.0 mol% or more, more preferably 95.0 mol% or more, and particularly preferably 97.0 mol% or more. There is no particular limit to the upper limit of the hydrogenation rate, but the upper limit may be 99.9 mol% or 99.5 mol%. When the hydrogenation rate of the polymer block (B) in the hydrogenated block copolymer (a) is within the above range, the copolymer has excellent heat resistance and weather resistance. In this specification, the "hydrogenation rate" refers to the rate of hydrogenation obtained by dissolving the copolymer in CDCl3 before and after hydrogenation. 1The H-NMR spectrum is measured [apparatus: AVANCE 400 Nanobay (Bruker), measurement temperature: 30°C], and the hydrogenation rate is calculated from the ratio of the peak area derived from the residual olefins, such as isoprene or butadiene, to the peak area derived from ethylene, propylene, and butylene.

[0025] Furthermore, polymer block (B) may contain structural units derived from polymerizable monomers other than butadiene and isoprene, as long as the effects of the present invention are not impaired. Examples of other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, and vinylanthracene; methyl methacrylate; methyl vinyl ether; N-vinylcarbazole; β-pinene; 8,9-p-menthene; dipentene; methylenenorbornene; and 2-methylenetetrahydrofuran. When the polymer block (B) contains structural units derived from polymerizable monomers other than butadiene and isoprene, the content thereof is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on the total mass of the polymer block (B). When the polymer block (B) contains structural units derived from polymerizable monomers other than butadiene and isoprene, the bonding form is not particularly limited and may be either random or tapered.

[0026] <Bonding type between polymer block (A) and polymer block (B)> The bonding form of the hydrogenated block copolymer (a) is not particularly limited as long as the polymer block (A) and the polymer block (B) are bonded together, and examples thereof include linear, branched, radial, etc. These may be used alone or in combination of two or more. Among these, linear is preferred. Specific examples of linear bond forms include a diblock copolymer represented by AB and a triblock copolymer represented by BAB, where A represents polymer block (A) and B represents polymer block (B). Among these, the diblock copolymer (AB) is preferred from the viewpoint of ease of production. Here, in this specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as a single polymer block. Accordingly, polymer blocks that should strictly be expressed as YXY (X represents a coupling residue), including the above examples, are expressed as Y as a whole, unless there is a particular need to distinguish them from a single polymer block Y. In this specification, since this type of polymer block containing a coupling agent residue is treated as above, for example, a block copolymer containing a coupling agent residue and that should strictly be expressed as BAXAB (X represents a coupling agent residue) is expressed as BAB and treated as an example of a triblock copolymer.

[0027] Furthermore, the hydrogenated block copolymer (a) may contain a polymer block (C) containing a polymerizable monomer other than the polymer block (A) and the polymer block (B) within a range that does not impair the object of the present invention. The polymer block (C) is not particularly limited, but in a preferred embodiment, the polymer block (C) is mainly composed of isoprene (Ip) units. Here, "mainly composed of" means that the polymer block (C) contains 50% by mass or more of isoprene units (Ip) based on the total mass of the polymer block (C). The content of isoprene units (Ip) in the polymer block (C) is preferably 70% by mass or more, more preferably 90% by mass or more, based on the total mass of the polymer block (C), and may have an upper limit of 100% by mass. The conjugated diene compound constituting the polymer block (C) mainly contains isoprene, and may further contain at least one selected from, for example, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. When the polymer block (C) is mainly composed of isoprene units (Ip), its degree of vinylation is not particularly limited, but is preferably 20% or less, more preferably 2 to 15%, and particularly preferably 5 to 10%. When the degree of vinylation of the polymer block (C) is within the above range, the dropping point and viscosity of the gel composition tend to be increased. As in the case of polymer block (B), the content of vinyl bonds in the total bond form of polymer block (C) is called the vinylation degree (%), and the contents of 1,2-bonds and 3,4-bonds are 1 It can be calculated by H-NMR measurement.

[0028] Similarly to the polymer block (B), the carbon-carbon double bonds of the polymer block (C) are preferably hydrogenated from the viewpoint of heat resistance and weather resistance. The hydrogenation rate (hydrogenation ratio) of the polymer block (C) in the hydrogenated block copolymer (a) is not particularly limited, but is preferably 80.0 mol% or more, more preferably 85.0 mol% or more, and particularly preferably 90.0 to 100.0 mol%. When the hydrogenation rate of the polymer block (C) in the hydrogenated block copolymer (a) is within the above range, the heat resistance and weather resistance tend to be excellent.

[0029] When polymer block (A) is represented by A, polymer block (B) by B, and polymer block (C) by C, examples of the block copolymer structure include a triblock copolymer represented by ABC, a tetrablock copolymer represented by BACB, and a tetrablock copolymer represented by BABC.

[0030] A specific example of the hydrogenated block copolymer (a) is a polystyrene-hydrogenated butadiene / isoprene copolymer diblock copolymer (hereinafter sometimes referred to as "SEEP"), which is presumed to have a structure represented by the following general formula (1), from the viewpoint of increasing the dropping point and viscosity of the gel composition. In formula (1), the isoprene units are shown with 1,4-bonds for convenience, but as mentioned above, the isoprene units may be 1,2-bonds, 3,4-bonds, or 1,4-bonds. Similarly, in formula (1), the butadiene units are shown with 1,4-bonds for convenience, but as mentioned above, the butadiene units may be 1,2-bonds or 1,4-bonds. [ka]

[0031] In the above formula (1), i, k, l, and m each represent an integer of equal to or greater than 1. In the above formula (1), the order of the isoprene unit and the butadiene unit is random.

[0032] The hydrogenated block copolymer (a) may have one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group, in the molecular chain and / or at the molecular terminal, as long as the effects of the present invention are not impaired.

[0033] <Physical properties of block copolymers> The weight-average molecular weight of the block copolymer before hydrogenation is preferably 20,000 to 500,000, more preferably 50,000 to 400,000, even more preferably 90,000 to 300,000, and particularly preferably 130,000 to 250,000. If the weight-average molecular weight of the block copolymer before hydrogenation is 20,000 or more, it is possible to adjust the viscosity to a level suitable for the gel composition, while if it is 500,000 or less, the time required to dissolve the hydrogenated block copolymer (a) in the base oil (b) is shortened, making it possible to easily produce the gel composition. The "weight average molecular weight" of the block copolymer before hydrogenation is the weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC) measurement, as described above.

[0034] The weight-average molecular weight of the hydrogenated block copolymer (a) is preferably 20,000 to 500,000, more preferably 50,000 to 400,000, even more preferably 90,000 to 300,000, and particularly preferably 130,000 to 250,000. When the weight-average molecular weight of the hydrogenated block copolymer (a) is 20,000 or more, it becomes possible to adjust the viscosity to a level suitable for the gel composition, while when it is 500,000 or less, the time required to dissolve the hydrogenated block copolymer (a) in the base oil (b) becomes shorter, and the gel composition can be easily produced. The "weight average molecular weight" of the hydrogenated block copolymer (a) is, as described above, a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC), and more specifically, a value measured according to the method described in the Examples.

[0035] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (a) is not particularly limited, but from the viewpoint of improving the dropping point of the gel composition, it is preferably 1.0 to 1.4, more preferably 1.0 to 1.3, even more preferably 1.0 to 1.2, and particularly preferably 1.0 to 1.1. The molecular weight distribution (Mw / Mn) is a value calculated from Mw and Mn determined as standard polystyrene equivalent molecular weights by gel permeation chromatography (GPC).

[0036] <Method for producing hydrogenated block copolymer (a)> Examples of methods for producing the hydrogenated block copolymer (a) include solution polymerization, emulsion polymerization, and solid-phase polymerization. Among these, solution polymerization is preferred. Known methods, such as ionic polymerization (e.g., anionic polymerization, cationic polymerization, etc.) and radical polymerization, can be used, with anionic polymerization being particularly preferred. In anionic polymerization, a mixture of an aromatic vinyl compound, butadiene, and isoprene is sequentially added in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base, to obtain a block copolymer, which is then hydrogenated to obtain the hydrogenated block copolymer (a). The method of sequentially adding a mixture of an aromatic vinyl compound, butadiene, and isoprene may involve adding an aromatic vinyl compound and polymerizing the mixture, followed by adding a mixture of butadiene and isoprene and polymerizing the mixture, or may involve adding a mixture of butadiene and isoprene and polymerizing the mixture, followed by adding an aromatic vinyl compound and polymerizing the mixture.

[0037] Examples of organolithium compounds used as anionic polymerization initiators in the above method include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium; and dilithium compounds such as tetraethylenedilithium. The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction, and examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatic hydrocarbons such as benzene, toluene, and xylene; etc. The polymerization reaction is usually carried out at 0 to 100°C for 0.5 to 50 hours. The Lewis base plays a role in controlling the microstructure of butadiene units and isoprene units. Examples of such Lewis bases include dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, pyridine, N,N,N',N'-tetramethylethylenediamine, trimethylamine, and N-methylmorpholine. One Lewis base may be used alone, or two or more Lewis bases may be used in combination.

[0038] After polymerization is carried out by the above-mentioned method, an active hydrogen compound such as an alcohol, a carboxylic acid, or water is added to terminate the polymerization reaction, and the resulting product can be hydrogenated in an inert organic solvent in the presence of a hydrogenation catalyst according to a known method to give a hydrogenated product. The hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst under a hydrogen pressure of preferably 0.1 to 20 MPa, more preferably 0.5 to 15 MPa, even more preferably 0.5 to 10 MPa, and particularly preferably 0.5 to 5 MPa at a reaction temperature of preferably 20 to 250°C, more preferably 50 to 180°C, even more preferably 70 to 180°C, and particularly preferably 70 to 100°C for a reaction time of usually 0.1 to 100 hours, and preferably 1 to 50 hours.

[0039] Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts in which a metal such as platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), or nickel (Ni) is supported on a carrier such as carbon, alumina, or diatomaceous earth; Ziegler catalysts containing a combination of a transition metal compound such as nickel octoate with an alkylaluminum compound, an alkyllithium compound, or the like; and metallocene catalysts containing a combination of a bis(cyclopentadienyl) compound of a transition metal such as titanium, zirconium, or hafnium with a metal such as lithium, sodium, potassium, aluminum, zinc, or magnesium.

[0040] The hydrogenated block copolymer (a) thus obtained can be obtained in the form of crumbs or powder by, if necessary, removing the catalyst by washing with water, pouring the hydrogenation reaction liquid into methanol or the like to precipitate and coagulate, followed by heating or drying under reduced pressure, or by pouring the polymerization reaction liquid into boiling water to remove the solvent by azeotropy (so-called steam stripping), followed by heating or drying under reduced pressure. When the hydrogenated block copolymer (a) is in the form of crumbs or powder, the mixing time during the production of a gel composition can be shortened, and the gel composition can be produced efficiently in a short time. Furthermore, producing the gel composition in a short time suppresses deterioration of the gel composition due to heat during mixing, and the gel composition can be produced without impairing the physical properties of the gel composition, such as the dropping point. The hydrogenated block copolymer (a) can be produced, for example, according to the method described in JP-A-10-67894 and WO 2009 / 031625.

[0041] [Gel composition] The gel composition of the present invention contains the hydrogenated block copolymer (a) of the present invention and a base oil (b). The base oil (b), other components, and the composition of the gel composition will be described below.

[0042] <Base oil (b)> Examples of the base oil (b) used in the present invention include mineral oils, synthetic oils, and vegetable oils. Examples of mineral oils include paraffinic mineral oils obtained by conventional refining methods such as solvent refining and hydrogenation refining; naphthenic mineral oils; waxes produced by the Fischer-Tropsch process (gas-to-liquid wax); and mineral oils produced by isomerizing wax. Examples of synthetic oils include hydrocarbon synthetic oils and ether synthetic oils. Examples of hydrocarbon synthetic oils include α-olefin oligomers such as polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, and ethylene-propylene copolymer, or hydrogenated versions thereof; alkylbenzene; and alkylnaphthalene. Examples of ether synthetic oils include polyoxyalkylene glycol and polyphenyl ether. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and peanut oil. The mineral, synthetic, and vegetable oils used in the present invention are classified into Groups I, II, III, IV, and V of the American Petroleum Institute (API) base oil classification.

[0043] The base oil (b) may be one selected from mineral oils, synthetic oils, and vegetable oils, or a mixture of two or more mineral oils, two or more synthetic oils, two or more vegetable oils, or one or more mineral oils, synthetic oils, and vegetable oils. When the gel composition of the present invention is used as part or all of a cable filler described below, mineral oil is preferred from the viewpoint of obtaining a gel composition having a viscosity suitable for use as a cable filler even when the blending ratio of hydrogenated block copolymer (a) in the gel composition is low, and at least one selected from paraffinic mineral oils and naphthenic mineral oils is more preferred. Furthermore, paraffinic mineral oils are even more preferred from the viewpoint of making the polymer block (A) in the hydrogenated block copolymer (a) less susceptible to plasticization, thereby improving the dropping point of the gel composition. Furthermore, paraffinic mineral oils classified as Group II and Group III are preferred because they have low sulfur content and high saturates, and mineral oils classified as Group III are particularly preferred.

[0044] When the gel composition of the present invention is used as part or all of a cosmetic product, the base oil (b) may be one selected from mineral oils, synthetic oils, and vegetable oils, or a mixture of two or more mineral oils, two or more synthetic oils, and two or more vegetable oils, or a mixture of one or more mineral oils, synthetic oils, and vegetable oils. From the viewpoint of purity, mineral oils or synthetic oils of Groups III, IV, and V are preferred.

[0045] When the gel composition of the present invention is used as part or all of a lubricating oil, the base oil (b) may be one selected from mineral oil, synthetic oil, and vegetable oil, or may be a mixture of two or more mineral oils, two or more synthetic oils, and two or more vegetable oils, or one or more mineral oils, synthetic oils, and vegetable oils, but mineral oil is preferred from an economical standpoint.

[0046] When the gel composition of the present invention is used as part or all of a grease, the base oil (b) may be one selected from mineral oils, synthetic oils, and vegetable oils, or may be a mixture of two or more mineral oils, two or more synthetic oils, and two or more vegetable oils, or one or more mineral oils, synthetic oils, and vegetable oils. However, base oils classified as Group I, Group II, and Group III are preferred because the raw materials are easily available, and base oils classified as Group II and Group III are more preferred because they have a low sulfur content and a high saturated content. It is further preferred that the base oils classified as Group II and Group III are mineral oils classified as Group II and Group III, and it is even more preferred that they are mineral oils classified as Group II. Furthermore, poly-α-olefins (abbreviated as PAO) classified into the above-mentioned Group IV can also be used.

[0047] The kinematic viscosity at 40°C of the base oil (b) can be appropriately selected depending on the intended use of the resulting grease composition, but is preferably 5 to 1,000 mm 2 / s, more preferably 10 to 500 mm 2 / s, more preferably 20 to 200 mm 2 / s, particularly preferably 25 to 50 mm 2 / s.

[0048] When the gel composition of the present invention is used as part or all of a grease, the content of base oil (b) is preferably 70 to 98 mass%, more preferably 75 to 97 mass%, even more preferably 80 to 96 mass%, and particularly preferably 85 to 95 mass%, based on 100 mass% of the total amount of the gel composition.

[0049] The base oil (b) in the present invention preferably contains paraffin or a combination of paraffin and naphthene, and the mass ratio of paraffin to naphthene [paraffin / naphthene] is preferably 10 / 90 to 100 / 0. When the mass ratio of paraffin to naphthene is within the above range, the polymer block (A) in the hydrogenated block copolymer (a) is less likely to be plasticized. When the gel composition of the present invention is used as part or all of a cable filler, from the viewpoint of improving the dropping point of the gel composition, the mass ratio of paraffin to naphthene [paraffin / naphthene] is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 90 / 10, even more preferably 30 / 70 to 90 / 10, even more preferably 40 / 60 to 90 / 10, even more preferably 50 / 50 to 90 / 10, even more preferably 60 / 40 to 90 / 10, and particularly preferably 60 / 40 to 80 / 20.

[0050] When the gel composition of the present invention is used as part or all of a cosmetic or lubricating oil, the base oil (b) preferably contains paraffin or a combination of paraffin and naphthene, and the mass ratio of paraffin to naphthene [paraffin / naphthene] is preferably 10 / 90 to 100 / 0, more preferably 20 / 80 to 100 / 0, even more preferably 30 / 70 to 100 / 0, even more preferably 40 / 60 to 100 / 0, even more preferably 50 / 50 to 100 / 0, even more preferably 60 / 40 to 100 / 0, and particularly preferably 70 / 30 to 100 / 0.

[0051] When the gel composition of the present invention is used as part or all of a grease, from the viewpoints of the availability of the base oil (b), economic efficiency, and the oxidation stability of the grease, the mass ratio of paraffin to naphthene [paraffin / naphthene] is preferably 10 / 90 to 100 / 0, more preferably 20 / 80 to 100 / 0, even more preferably 30 / 70 to 100 / 0, even more preferably 40 / 60 to 100 / 0, even more preferably 50 / 50 to 100 / 0, even more preferably 60 / 40 to 100 / 0, even more preferably 70 / 30 to 100 / 0, and particularly preferably 70 / 30 to 90 / 10.

[0052] The viscosity index of the base oil (b) used in the present invention is preferably 70 or more, more preferably 80 or more, even more preferably 90 or more, particularly preferably 100 or more, and is preferably 150 or less, more preferably 145 or less, even more preferably 140 or less, even more preferably 135 or less, particularly preferably less than 120.

[0053] <Other ingredients> The gel composition of the present invention may contain other components as needed, such as antioxidants, surfactants, pour point depressants, antifoaming agents, gelling agents, viscosity index improvers, thickeners, water absorbents, flame retardants, fillers, tackifying resins, thixotropic agents, petroleum waxes, metal deactivators, copper passivators, friction modifiers, rust inhibitors, detergents and dispersants, extreme pressure agents, thickeners, etc. These additives may be used alone or in combination of two or more.

[0054] Examples of antioxidants include hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, sulfide antioxidants, and organic phosphoric acid antioxidants. Among these, hindered phenol antioxidants, aromatic amine antioxidants, and organic phosphoric acid antioxidants are preferred, and hindered phenol antioxidants are more preferred. These antioxidants may be used alone or in combination of two or more. When the gel composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 parts by mass, and particularly preferably 0.03 to 0.1 part by mass, per 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b).

[0055] The antioxidant may be added during the production of a gel composition or during the production of a hydrogenated block copolymer. When added during the production of a hydrogenated block copolymer, the antioxidant can be added and mixed into a solution of the copolymer after the polymerization reaction, hydrogenation reaction, or water washing. Alternatively, the antioxidant can be added and mixed into a hydrogenated block copolymer in a crumb or powder state. Among these, from the viewpoint of achieving more uniform mixing of the antioxidant and thereby suppressing thermal degradation of the hydrogenated block copolymer during the production of a gel composition, adding the antioxidant to a solution of the copolymer after the polymerization reaction, hydrogenation reaction, or water washing is preferred, and adding the antioxidant to a solution of the copolymer after the hydrogenation reaction or water washing is more preferred. Furthermore, suppressing thermal degradation of the hydrogenated block copolymer during the production of a gel composition allows the production of a gel composition without impairing its physical properties, such as the dropping point.

[0056] When the gel composition as a lubricating oil contains a viscosity index improver, the content of the viscosity index improver in the gel composition can be appropriately adjusted so that the viscosity and viscosity index of the lubricating oil fall within the desired range, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 10% by mass. If the content of the viscosity index improver in the gel composition is within the above range, the lubricating oil tends to have an excellent balance between performance and economy.

[0057] Examples of the thickener include one or more selected from soap-based thickeners and non-soap-based thickeners.

[0058] Examples of the soap-based thickener include metal soaps containing salts of metals such as lithium, calcium, aluminum, sodium, potassium, barium, and strontium. More specifically, examples thereof include simple soaps such as lithium soaps, calcium soaps, aluminum soaps, and sodium soaps; and complex soaps such as lithium complex soaps, calcium complex soaps, calcium sulfonate complex soaps, and aluminum complex soaps. The soap-based thickener is preferably one or more lithium soap-based thickeners selected from lithium soaps and lithium complex soaps; or one or more calcium soap-based thickeners selected from the group consisting of calcium soaps, calcium complex soaps, and calcium sulfonate complex soaps; and the lithium soap-based thickeners are more preferred.

[0059] The soap-based thickener can be obtained, for example, by saponifying one or more selected from carboxylic acids and carboxylic acid esters with a metal hydroxide. For example, the soap-based thickener can be produced by blending one or more selected from carboxylic acids and carboxylic acid esters with a metal hydroxide and saponifying the base oil (b) in the base oil (b). Alternatively, an aqueous solution of a metal hydroxide can be added to base oil (b) containing one or more selected from carboxylic acids and carboxylic acid esters, and heated as necessary to produce the soap-based thickener through saponification in the base oil (b). After adding the aqueous solution of a metal hydroxide and carrying out the saponification reaction, unnecessary water can be removed by evaporation or the like. Alternatively, a pressurized saponification method can be used in which pressure is applied during the saponification reaction.

[0060] Examples of the metal hydroxide include hydroxides of lithium, calcium, aluminum, sodium, potassium, barium, strontium, etc., and preferably at least one selected from the group consisting of lithium hydroxide, calcium hydroxide, and aluminum hydroxide, more preferably at least one selected from lithium hydroxide and calcium hydroxide, and even more preferably lithium hydroxide. Examples of the carboxylic acid include crude fatty acids obtained by hydrolyzing fats and oils to remove glycerin, fatty acids such as monocarboxylic acids such as stearic acid, and monohydroxycarboxylic acids such as 12-hydroxystearic acid; dibasic acids such as azelaic acid; and aromatic carboxylic acids such as terephthalic acid, salicylic acid, and benzoic acid.

[0061] The lithium soap-based thickener is not particularly limited, and any lithium soap-based thickener known as a grease thickener can be used, including, for example, lithium soap, which is a lithium salt obtained by reacting lithium hydroxide with a fatty acid, and lithium complex soap, which is obtained by reacting lithium hydroxide with a fatty acid and an acid other than a fatty acid, such as one or more selected from dibasic acids, phosphoric acids, and aromatic carboxylic acids. Fatty acids having 10 to 24 carbon atoms are preferred examples of the fatty acid, and examples of the lithium soap-based thickener include lithium stearate, lithium behenate, and lithium 12-hydroxystearate. Examples of the lithium soap-based thickener include complex amide lithium soaps in which an aliphatic monoamine is used in addition to the above-mentioned components and an amide bond is introduced into the molecule. The soap-based thickeners may be used alone or in combination of two or more.

[0062] Examples of the non-soap thickener include urea thickeners made of urea compounds such as polyurea, fluorine thickeners made of fluororesins such as polytetrafluoroethylene, and organic thickeners such as sodium terephthalamate; and inorganic thickeners typified by organo-clays such as organo-bentonite, silica, and the like. As the non-soap-based thickener, a urea-based thickener is preferred.

[0063] The urea-based thickener is not particularly limited, and any urea compound known as a grease thickener can be used, including, for example, urea-based compounds such as diurea compounds, triurea compounds, tetraurea compounds, and urea-urethane compounds obtained by reacting an isocyanate compound such as polyisocyanate with an amine compound such as monoamine. Among these, a preferred example is a diurea compound obtained by reacting a diisocyanate with a monoamine. Examples of the diisocyanate include phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, octadecane diisocyanate, decane diisocyanate, and hexane diisocyanate. Examples of the monoamine include aliphatic monoamines such as hexylamine, octylamine, dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, and octadecenylamine; alicyclic monoamines such as cyclohexylamine; and aromatic monoamines such as aniline and p-toluidine.

[0064] The urea-based thickener may be prepared, for example, by blending an isocyanate compound and an amine compound into base oil (b) and reacting the isocyanate compound with the amine compound in the base oil (b). Alternatively, a base oil (b) containing an isocyanate compound in advance and a base oil (b) containing an amine compound in advance may be mixed, and then the mixture may be heated as necessary to react the isocyanate compound with the amine compound in the base oil (b) to produce the urea compound. The urea-based thickeners may be used alone or in combination of two or more.

[0065] When the gel composition used as a grease contains a thickener, the content of the thickener in the gel composition can be adjusted appropriately so that the grease's mixed consistency, mixing stability, oil separation rate, and aqueous water resistance fall within the desired ranges, but is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, even more preferably 3 to 20% by mass, even more preferably 4 to 18% by mass, even more preferably 5 to 16% by mass, and particularly preferably 6 to 12% by mass. If the content of the thickener in the gel composition is within the above range, the grease tends to have an excellent balance between performance and economy.

[0066] <Content of hydrogenated block copolymer (a)> The content of the hydrogenated block copolymer (a) in the gel composition of the present invention is preferably 0.10 to 30.00 parts by mass, more preferably 0.25 to 27.00 parts by mass, even more preferably 0.50 to 25.00 parts by mass, even more preferably 0.75 to 23.00 parts by mass, even more preferably 0.20 to 5.00 parts by mass, and particularly preferably 0.30 to 4.00 parts by mass, relative to 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b).

[0067] When the gel composition of the present invention is used as a cable filler, the content of the hydrogenated block copolymer (a) in the gel composition of the present invention is preferably 1 to 20 parts by mass, more preferably 2 to 18 parts by mass, even more preferably 4 to 16 parts by mass, even more preferably 6 to 14 parts by mass, and particularly preferably 7 to 13 parts by mass, relative to 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b). When the content of the hydrogenated block copolymer (a) in the gel composition is within the above range, it becomes easy to fill the gel composition as a cable filler into a protective tube or a cable during cable production. Furthermore, when the gel composition of the present invention is used as a cosmetic, the content of the hydrogenated block copolymer (a) in the gel composition is preferably in the same range as when it is used as a cable filler. When the content of the hydrogenated block copolymer (a) in the gel composition is in the above range, it becomes easy to fill the cosmetic composition into a container during the production of the cosmetic, or to use the cosmetic composition.

[0068] When the gel composition of the present invention is used as a lubricating oil, the content of the hydrogenated block copolymer (a) in the gel composition is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, even more preferably 0.3 to 4.0 parts by mass, even more preferably 0.4 to 3.0 parts by mass, and particularly preferably 0.5 to 2.0 parts by mass, per 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b). When the content of the hydrogenated block copolymer (a) in the gel composition is within the above range, the lubricating oil tends to have an excellent balance between performance and economy.

[0069] When the gel composition of the present invention is used as a grease, the content of the hydrogenated block copolymer (a) in the gel composition is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, even more preferably 0.2 to 4.5 parts by mass, even more preferably 0.3 to 4.0 parts by mass, even more preferably 0.5 to 4.0 parts by mass, even more preferably 1.0 to 4.0 parts by mass, even more preferably 1.5 to 4.0 parts by mass, and particularly preferably 1.8 to 3.5 parts by mass, per 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b). When the content of the hydrogenated block copolymer (a) in the gel composition is within the above range, the grease tends to have an excellent balance between performance and economy.

[0070] <Base oil (b) content> The content of base oil (b) in the gel composition is preferably 70.00 parts by mass or more, more preferably 73.00 parts by mass or more, even more preferably 75.00 parts by mass or more, and particularly preferably 77.00 parts by mass or more, per 100 parts by mass of the total of hydrogenated block copolymer (a) and base oil (b), and the upper limit is preferably 99.90 parts by mass, more preferably 99.75 parts by mass, even more preferably 99.50 parts by mass, and particularly preferably 99.25 parts by mass.

[0071] When the gel composition of the present invention is used as a cable filler, the content of base oil (b) in the gel composition is preferably 80 parts by mass or more, more preferably 83 parts by mass or more, and particularly preferably 86 parts by mass or more, per 100 parts by mass of the total of hydrogenated block copolymer (a) and base oil (b), and the upper limit is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and particularly preferably 94 parts by mass or less. If the content of base oil (b) in the gel composition is within the above range, when the gel composition is used as a cable filler during cable production, the gel composition can be easily filled into a protective tube or cable.

[0072] When the gel composition of the present invention is used as a cosmetic, the content of base oil (b) in the gel composition is preferably 80 parts by mass or more, more preferably 83 parts by mass or more, and particularly preferably 86 parts by mass or more, per 100 parts by mass of the total of hydrogenated block copolymer (a) and base oil (b), and the upper limit is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and particularly preferably 94 parts by mass or less. When the content of base oil (b) in the gel composition is within the above range, it becomes easy to fill the cosmetic composition into a container or use it during the production of cosmetics.

[0073] When the gel composition of the present invention is used as a lubricating oil, the content of the base oil (b) in the gel composition is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, particularly preferably 96 parts by mass or more, relative to 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b), and the upper limit is preferably 99.9 parts by mass or less, more preferably 99.8 parts by mass or less, particularly preferably 99.7 parts by mass or less. When the content of the base oil (b) in the gel composition is within the above range, the lubricating oil tends to have an excellent balance between performance and economy.

[0074] When the gel composition of the present invention is used as a grease, the content of base oil (b) in the gel composition is preferably 90.0 parts by mass or more, more preferably 95.0 parts by mass or more, and particularly preferably 96.0 parts by mass or more, relative to 100 parts by mass of the total of the hydrogenated block copolymer (a) and the base oil (b), and the upper limit is preferably 99.9 parts by mass or less, more preferably 99.8 parts by mass or less, and particularly preferably 99.7 parts by mass or less. When the content of base oil (b) in the gel composition is within the above range, the grease tends to have an excellent balance between performance and economy.

[0075] <Method of manufacturing gel composition> The gel composition of the present invention can be produced by a production method well known in the art. For example, it can be produced by mixing the hydrogenated block copolymer (a), the base oil (b), and other components as needed. Mixing can be carried out using a well-known mixing device. More specifically, the hydrogenated block copolymer (a), the base oil (b), and, if necessary, other components are mixed in air or nitrogen at 100 to 200°C for 0.1 to 10 hours, and then, if necessary, placed under vacuum, followed by cooling, whereby the copolymer can be produced.

[0076] <Characteristics of the gel composition> (dropping point) By using the hydrogenated block copolymer (a) of the present invention, the dropping point of the gel composition (the temperature at which the gel composition changes from semi-solid to liquid) can be set to 195°C or higher, and can also be set to 197°C or higher, 200°C or higher, or even 205°C or higher. There is no particular upper limit to the dropping point, but it is usually 400°C or lower, and may be 300°C or lower. When the dropping point of the gel composition is within the above range, when used as a cable filler, the gel composition as a filler tends to exhibit the property of not flowing out from the protective tube or inside the cable over a wide range of temperatures, even if the protective tube is damaged. Furthermore, the gel composition can be easily used as a gel composition with excellent shape retention in a wide range of applications other than cable filler. The dropping point in this specification refers to a value measured by a method in accordance with JIS K 2220:2013, and specifically refers to a value measured by the measurement method described in the examples.

[0077] (consistency) By adjusting the consistency of the gel composition containing the hydrogenated block copolymer of the present invention to 360 to 430, when the gel composition of the present invention is used as a cable filler, it is possible to obtain a gel composition of appropriate hardness that easily protects the inside. From the above viewpoint, the consistency of the gel composition of the present invention is preferably 370 to 420, and more preferably 375 to 390. The consistency in this specification refers to a value measured according to a method in accordance with JIS K 2220:2013, and specifically refers to a value measured by the measurement method described in the examples.

[0078] (viscosity) When the gel composition of the present invention is used as a cable filler, 50 s of the gel composition of the present invention are used.-1 The viscosity under this shear rate condition is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, even more preferably 2,000 mPa·s or more, even more preferably 3,000 mPa·s or more, even more preferably 3,500 mPa·s or more, and particularly preferably 4,000 mPa·s or more, from the viewpoint of preventing the gel composition, which is a filler, from flowing out from the inside if the protective tube or cable is damaged, and is preferably 300,000 mPa·s or less, more preferably 20,000 mPa·s or less, even more preferably 18,000 mPa·s or less, and particularly preferably 16,000 mPa·s or less, from the viewpoint of easily filling the protective tube or cable with the gel composition during cable production. The viscosity in this specification refers to a value measured by a rheometer.

[0079] When the gel composition of the present invention is used as a cosmetic product, the gel composition is -1 From the viewpoint of facilitating filling the cosmetic composition into containers during cosmetic production or use, the viscosity under this shear rate condition is preferably 500 mPa·s or more and 100,000 mPa·s or less, more preferably 1,000 mPa·s or more and 50,000 mPa·s or less, even more preferably 2,000 mPa·s or more and 40,000 mPa·s or less, even more preferably 4,000 mPa·s or more and 30,000 mPa·s or less, still more preferably 9,000 mPa·s or more and 30,000 mPa·s or less, and particularly preferably 15,000 mPa·s or more and 25,000 mPa·s or less.

[0080] (Kinematic viscosity) When the gel composition of the present invention is used as a lubricating oil, its kinematic viscosity at 40°C is 40 to 300 mm 2 / sec range is preferable, and 50 to 150 mm 2 The kinematic viscosity at 100°C is more preferably in the range of 3 to 30 mm / sec. 2 / sec range is preferable, and 4 to 20 mm 2 / sec is more preferable. When the kinematic viscosity is within the above range, fuel consumption can be reduced. In the present invention, the kinematic viscosity is a value measured in accordance with JIS K2283:2000.

[0081] (mixing consistency) When the gel composition of the present invention is used as a grease, its worked consistency is preferably 85 to 475, more preferably 130 to 430, even more preferably 175 to 385, even more preferably 220 to 340, and particularly preferably 265 to 295. A low worked consistency can enhance the thickening effect. In the present invention, the worked consistency can be measured according to the method described in the examples.

[0082] (Increased consistency) When the gel composition of the present invention is used as a grease, the increase in consistency is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. A small increase in consistency can improve shear stability. In the present invention, the increase in consistency is the difference between the mixing stability and the mixing consistency. In the present invention, both the mixing stability and the mixing consistency can be measured according to the methods described in the Examples.

[0083] (Oil separation degree) When the gel composition of the present invention is used as a grease, the oil separation degree is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and particularly preferably 3.0% by mass or less. A low oil separation degree can improve oil retention. In the present invention, the oil separation degree can be measured according to the method described in the Examples.

[0084] [Cable filler, cable] The cable filler of the present invention contains the gel composition of the present invention, or may contain only the gel composition of the present invention. The gel composition of the present invention has a viscosity suitable for use as a cable filler, allows the gel composition to be easily filled into a protective tube or cable during cable production, has a high dropping point, and exhibits the property of preventing the filler from flowing out from the inside over a wide range of temperatures even if the protective tube or cable is damaged, and can also prevent water from penetrating into the inside, making it suitable as an internal cushioning material for cables such as optical fiber cables and electric cables.

[0085] The cable of the present invention contains the gel composition of the present invention, and for example, the gel composition of the present invention is filled between a protective tube and a cable, or around the optical fiber core in a cable. As described above, the gel composition of the present invention has sufficient elasticity to protect cables, etc., and can be easily filled into a protective tube or a cable, and has a viscosity that prevents the filler from flowing out from the inside if the protective tube or cable is damaged. Furthermore, even if the protective tube or cable is damaged, it can prevent water from entering the inside. Therefore, the cable of the present invention can be particularly suitably used as an optical fiber cable.

[0086] [cosmetics] The cosmetic product of the present invention contains the gel composition of the present invention, and may contain only the gel composition of the present invention. The gel composition of the present invention can be used in the cosmetic composition that constitutes the cosmetic of the present invention. Cosmetics, for example, hair makeup products such as shampoos, hair setting gels or lotions, blow-drying lotions, fixing and styling agents; Skin makeup products such as foundation, eye shadow, blusher, concealer, compact powder, and makeup base; Lip makeup products such as lipstick, liquid lipstick, and lip gloss; Cleansing products such as facial cleansers and makeup removers; Cream products such as petrolatum cream, hand cream, and ultrasound diagnostic cream;

[0087] [Lubricating oil] The lubricating oil of the present invention contains the gel composition of the present invention, and may contain only the gel composition of the present invention. The gel compositions of the present invention can be used in lubricating oil compositions that comprise the lubricating oils of the present invention, such as engine oils, automatic transmission fluids, gear lubricants, and hydraulic oils.

[0088] [Grease] The grease of the present invention contains the gel composition of the present invention, and preferably contains only the gel composition of the present invention. The gel composition of the present invention can be used in the grease composition constituting the grease of the present invention, for example, grease for sliding members.

[0089] A sliding member to which the grease for sliding members is applied has the grease on its sliding surface, and the sliding surface slides in the presence of the grease composition. The sliding member is preferably one whose sliding surface is coated with the grease composition.

[0090] The sliding member preferably contains at least one selected from metal and resin. That is, the material of the sliding member is preferably at least one selected from metal and resin. The sliding member may be a metal sliding member, or a resin sliding member such as plastic or rubber, or may be a sliding member manufactured using both metal and resin.

[0091] The sliding member is not particularly limited as long as it is used with grease applied to the sliding surface, and examples thereof include door panels, instrument panels, door locks, gears, outboard joints, inboard joints, universal joints, flexible joints, belt tensioners, fixing belts, pressure belts, pads, timing belts, conveyor belts, body seals for sunroofs, glass runs, weather strips, oil seals, packings, wiper blades, doctor blades, charging rollers, developing rollers, toner supply rollers, transfer rollers, heat rollers, pressure rollers, cleaning blades, Examples include paper feed rollers, transport rollers, intermediate transfer belts, intermediate transfer drums, heat belts, solenoid valves, electric valves, crankshafts, compressor shafts, slide bearings, oil pump gears, pistons, piston rings, piston pins, gaskets, guide rails, seatbelt buckles, brake pads, brake pad clips, brake shims, brake insulators, hinges, screws, pressure pads, air cylinders, electric cylinders, electric actuators, and other sliding parts for automobiles, copiers, printers, and industrial machinery (including semiconductor manufacturing equipment and light emitting device / display manufacturing equipment).

[0092] The grease is also suitable as a grease composition for rotary sliding members that perform rotary motion. The rotary sliding member is not particularly limited as long as it is accompanied by rotary motion, and examples thereof include bearings, gears, rotary shafts, belts, heat rollers, steering rollers, and the like.

[0093] The applications of the sliding member are not particularly limited, and the sliding member can be used for, for example, home appliances, ships, railways, aircraft, machinery (including industrial production equipment), structures, automobile repair, automobiles, construction, building materials, textiles, leather, stationery, woodworking, furniture, miscellaneous goods, steel plates, cans, electronic substrates, electronic components, printing, etc. Among these, the sliding member is useful for applications in automobiles and industrial machinery. That is, the sliding member is preferably an automobile part or an industrial machinery part. Similarly, the grease according to one embodiment of the present invention can be suitably used in automobiles and industrial machinery. Furthermore, as described above, the grease according to one aspect of the present invention is also useful for reducing noise, and therefore can be suitably used, for example, in mechanical devices or drive devices equipped with motors, and more specifically, can be suitably used in motor components.

[0094] [Other uses of gel composition] Furthermore, the gel composition of the present invention can be further used as an asphalt modifier, adhesive, pressure sensitive adhesive, resin modifier, compatibilizer, sealant, coating material, molded article, fiber / nonwoven fabric, drilling fluid, etc. [Example]

[0095] [Examples 1 to 11 and Comparative Examples 1 to 11] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples at all. The hydrogenated block copolymers (SEEP-1 to SEP-3, SEP-1 to SEP-3) produced in each Production Example were evaluated for (1) weight-average molecular weight (Mw) and number-average molecular weight (Mn), (2) content (styrene content) of polymer block (A) and molar ratio of butadiene units (Bd) to isoprene units (Ip) in polymer block (B), and (3) degree of vinylation of polymer block (B) according to the following evaluation methods. The gel compositions containing the hydrogenated block copolymers obtained in each production example were evaluated for (4) dropping point, (5) consistency (mixed consistency), (6) viscosity and thickening effect, (7) kinematic viscosity, (8) viscosity index, (9) mixing stability, (10) oil separation rate, and (11) water washout resistance according to the following evaluation methods. The gel compositions used for each evaluation were prepared as described in Examples 1 to 11 and Comparative Examples 1 to 11.

[0096] (1) Weight average molecular weight (Mw) and number average molecular weight (Mn) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of each hydrogenated block copolymer and polymer block (A) were calculated by gel permeation chromatography (GPC) measurement under the following conditions.

[0097] <GPC Measuring Apparatus and Measurement Conditions> · Apparatus: GPC apparatus "HLC-8020" (manufactured by Tosoh Corporation) · Separation column: Two columns of "TSKgel G4000HX" (manufactured by Tosoh Corporation) were connected in series · Eluent: Tetrahydrofuran · Eluent flow rate: 0.7 mL / min · Sample concentration: 5 mg / 10 mL · Column temperature: 40 °C · Detector: Differential refractive index (RI) detector · Calibration curve: Prepared using standard polystyrene

[0098] (2) Content of polymer block (A) (styrene content), and molar ratio of butadiene unit (Bd) to isoprene unit (Ip) in polymer block (B) The copolymer after hydrogenation was dissolved in CDCl3 1 1H-NMR spectrum was measured [Apparatus: "AVANCE 400 Nanobay" (manufactured by Bruker), Measurement temperature: 30 °C], and the content of polymer block (A) (styrene content) was calculated from the obtained spectrum. On the other hand, the copolymer before hydrogenation was dissolved in CDCl3 and the same 1 1H-NMR spectrum was measured, and the molar ratio of butadiene unit (Bd) to isoprene unit (Ip) in polymer block (B) was calculated from the obtained spectrum.

[0099] (3) Degree of vinylation of polymer block (B) The block copolymer before hydrogenation was dissolved in CDCl3 1H-NMR measurement was performed [apparatus: "AVANCE 400 Nanobay" (manufactured by Bruker), measurement temperature: 30°C]. The degree of vinylation (total content of 3,4-bond units and 1,2-bond units) was calculated from the ratio of the peak area corresponding to the 3,4-bond units and 1,2-bond units in the isoprene units and the 1,2-bond units in the butadiene units to the total peak area of ​​the isoprene units and / or butadiene units.

[0100] (4) Dropping Point of Gel Composition (Examples 1 to 3, Comparative Examples 1 to 3 and 6) The dropping point was measured according to a method in accordance with JIS K 2220: 2013. That is, the dropping point was measured by placing the gel composition in a specified sample container, raising the temperature at a rate of 4 to 7°C / min until the temperature reached a temperature 17°C lower than the dropping point, and then continuing to raise the temperature at a rate of 1.0 to 1.5°C / min, and determining the temperature at which the gel composition softened and dropped through the hole in the sample container.

[0101] (5) Consistency of Gel Composition (Worked Consistency) (Examples 1 to 3, 10 and 11, Comparative Examples 1 to 3, 6, and 9 to 11) The consistency (working consistency) of the gel composition was measured in accordance with item 7 of JIS K 2220:2013.

[0102] (6) Viscosity and Thickening Effect of Gel Composition (Examples 1 to 6, Comparative Examples 1 to 4 and 6 to 7) The viscosity of the gel composition was measured at 25°C for 50 seconds using a rheometer (R / S+ RHEOMETER, manufactured by BROOKFIELD). -1 More specifically, about 30 mL of the gel composition was placed in a sample chamber (manufactured by Brookfield, MB3-25F), which was then attached to a rheometer body equipped with a spindle (manufactured by Brookfield, CC3-25). -1 The measurement was then performed for 300 seconds at 1 s and stabilized. -1 From the 50s -1 After raising it for 120 seconds, -1 to 1s -1(2) The shear rate was reduced to 1 s -1 From the 50s -1 After raising it for 120 seconds, -1 to 1s -1 (3) The shear rate was then reduced to 1 s -1 From the 50s -1 After raising it for 120 seconds, -1 to 1s -1 The shear rate in (3) was reduced to 1 s over 120 seconds. -1 From the 50s -1 The measurement was performed over a 120-second period. -1 The viscosity at the shear rate condition was used. Furthermore, for Examples 4 to 6 and Comparative Examples 4, 6 and 7, the thickening effect was calculated using the following formula. Thickening effect = (viscosity of the gel composition obtained above) ÷ (kinematic viscosity of base oil (b) at 40°C)

[0103] (7) Dynamic Viscosity of Gel Composition (Examples 7 to 9, Comparative Examples 5 and 8) The kinematic viscosity of the gel composition was measured at 40°C and 100°C in accordance with JIS K2283:2000.

[0104] (8) Viscosity Index of Gel Composition (Examples 7 to 9, Comparative Examples 5 and 8) The viscosity index of the gel composition was measured in accordance with JIS K2283:2000.

[0105] (9) Mixing Stability of Composition (Examples 10 and 11, Comparative Examples 9 to 11) The mixing stability of the composition was measured in accordance with item 15 of JIS K2220:2013.

[0106] (10) Oil Separation Rate of Composition (Examples 10 and 11, Comparative Examples 9 to 11) The oil separation rate of the composition was measured in accordance with item 11 of JIS K2220:2013.

[0107] (11) Washing Resistance of Composition (Examples 10 and 11, Comparative Examples 9 to 11) The water wash resistance of the composition was measured in accordance with item 16 of JIS K2220:2013.

[0108] <Hydrogenated Block Copolymer> The hydrogenated block copolymers (SEEP-1 to 4, SEP-1 to 3) produced in the following Production Examples 1 to 7 are listed as Examples 1 to 11 and Comparative Examples 1 to 11. Table 1 shows the properties of each hydrogenated block copolymer. <<Production Example 1: Production of hydrogenated block copolymer (SEEP-1)>> A pressure vessel purged with dry nitrogen was charged with 2,720 g of cyclohexane, and 5.0 mL of sec-butyllithium (1.0 mol / L, cyclohexane solution) was used as an anionic polymerization initiator. 180 g of styrene, 133 g of 1,3-butadiene, and 167 g of isoprene were sequentially added and polymerized to obtain a reaction solution containing a diblock copolymer. The polymerization of styrene was carried out at 50°C for 1.5 hours, and the polymerization of the 1,3-butadiene / isoprene mixture was carried out at 50°C for 4.5 hours. A Ziegler hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to this reaction solution under a hydrogen atmosphere, and the reaction was carried out for 4 hours under conditions of a hydrogen pressure of 1.0 MPa and 80°C. The reaction solution was then allowed to cool and the pressure was released, after which the catalyst was removed by washing with water and the mixture was dried in a vacuum to obtain a hydrogenated product of polystyrene-polybutadiene / isoprene diblock copolymer (hereinafter also referred to as "SEEP-1"). The physical properties of the obtained hydrogenated product (SEEP-1) were evaluated according to the methods described above. The results are shown in Table 1. Note that precipitation and coagulation procedures were performed before the vacuum drying, and the obtained hydrogenated product was in the form of crumbs, with a hydrogenation rate of 99.5 mol%. The "hydrogenation rate" is the rate at which the hydrogenated product obtained in Production Example 1 is dissolved in CDCl3. 1H-NMR spectra were measured [apparatus: AVANCE 400 Nanobay (Bruker), measurement temperature: 30°C], and the hydrogenation rate was calculated from the ratio of the peak area derived from the residual olefin of isoprene or butadiene to the peak area derived from ethylene, propylene, and butylene. The same applies to the hydrogenated products obtained in Production Examples 2 to 6.

[0109] <<Production Example 2: Production of hydrogenated block copolymer (SEEP-2)>> Hydrogenated block copolymer (a) (hereinafter also referred to as "SEEP-2") was produced in the same manner as in Production Example 1, except that 4.0 mL of sec-butyllithium (1.0 mol / L, cyclohexane solution) was used, the amount of styrene was 144 g, the amount of 1,3-butadiene was 149 g, and the amount of isoprene was 188 g, so as to obtain the weight-average molecular weight shown in Table 1. The physical properties of the obtained hydrogenated product were evaluated according to the above-mentioned methods. The results are shown in Table 1. The obtained hydrogenated product was in the form of crumbs, and the hydrogenation rate was 99.7 mol%.

[0110] <<Production Example 3: Production of hydrogenated block copolymer (SEEP-3)>> Hydrogenated block copolymer (a) (hereinafter also referred to as "SEEP-3") was produced in the same manner as in Production Example 1, except that 3.4 mL of sec-butyllithium (1.0 mol / L, cyclohexane solution) was used, the amount of styrene was 144 g, the amount of 1,3-butadiene was 151 g, and the amount of isoprene was 185 g, so as to obtain the weight-average molecular weight shown in Table 1. The physical properties of the obtained hydrogenated product were evaluated according to the above-mentioned methods. The results are shown in Table 1. The obtained hydrogenated product was in the form of crumbs, and the hydrogenation rate was 99.3 mol%.

[0111] <<Production Examples 4 to 6: Production of hydrogenated block copolymers (SEP-1, SEP-2, and SEP-3)>> Hydrogenated block copolymers (hereinafter also referred to as "SEP-1," "SEP-2," or "SEP-3") were produced in the same manner as in Production Example 1, except that 1,3-butadiene was not used and the amount of styrene, the amount of isoprene, and the reaction conditions were changed so as to obtain the weight-average molecular weights shown in Table 1. The physical properties of the obtained hydrogenated products were evaluated according to the methods described above. The results are shown in Table 1. The obtained hydrogenated products were in the form of crumbs, and the hydrogenation rates were 99.4 mol% ("SEP-1"), 99.2 mol% ("SEP-2"), and 99.6 mol% ("SEP-3"), respectively.

[0112] <<Production Example 7: Production of hydrogenated block copolymer (SEEP-4)>> Hydrogenated block copolymer (a) (hereinafter also referred to as "SEEP-4") was produced in the same manner as in Production Example 1, except that 5.5 mL of sec-butyllithium (1.0 mol / L, cyclohexane solution) was used, the amount of styrene was 199 g, the amount of 1,3-butadiene was 125 g, and the amount of isoprene was 157 g, so as to obtain the weight-average molecular weight shown in Table 1. The physical properties of the obtained hydrogenated product were evaluated according to the above-mentioned methods. The results are shown in Table 1. The obtained hydrogenated product was in the form of crumbs, and the hydrogenation rate was 99.4 mol%.

[0113] <Gel composition> Example 1 Seven parts by mass of the hydrogenated block copolymer (SEEP-1) produced in Production Example 1, 93 parts by mass of base oil (component ratio: paraffin 66 (% Cp), naphthene 34 (% Cn), aroma 0 (% Ca); viscosity index: 115; color: transparent), and 0.05 parts by mass of an antioxidant (hindered phenol-based antioxidant: ADEKA AO-60) were mixed under nitrogen at 150°C for 3 hours using a Three-One Motor manufactured by Shinto Chemical Co., Ltd. The mixture was then cooled to room temperature to prepare gel composition 1. The dropping point, consistency, and viscosity of the obtained gel composition 1 were measured according to the above-mentioned methods. The results are shown in Example 1 of Table 1.

[0114] <Examples 2 to 3, Comparative Examples 1 to 3 and 6> Gel compositions 2 to 6 and 15 were produced in the same manner as in Example 1, except that the hydrogenated block copolymer (SEEP-1) produced in Production Example 1 was replaced with the hydrogenated block copolymers (SEEP-2, SEEP-3, SEP-1, SEP-2, SEP-3, or SEEP-4) produced in Production Examples 2 to 7. The dropping point, consistency, and viscosity of the resulting gel compositions 2 to 6 and 15 were measured according to the methods described above. The results are shown in Table 1 for Examples 2 to 3 and Comparative Examples 1 to 3 and 6.

[0115] [Table 1]

[0116] From Table 1, we can see the following: The gel compositions of Examples 1 to 3 had high dropping points and excellent heat resistance, whereas the gel compositions of Comparative Examples 1 to 3 and 6 had low dropping points and poor heat resistance. Furthermore, the gel compositions of Examples 2 and 3 had a lower consistency than the gel composition of Example 1, and gel compositions with appropriate hardness were obtained.

[0117] Example 4: Suitable as a cosmetic gel composition 10 parts by mass of the hydrogenated block copolymer (SEEP-1) produced in Production Example 1, a kinematic viscosity at 40°C of 31 mm 2 90 parts by mass of a base oil having a viscosity of 1 / s (component ratio: paraffin 100 (% Cp), naphthene 0 (% Cn), aroma 0 (% Ca); viscosity index: 135; color: transparent) and 0.05 parts by mass of an antioxidant (hindered phenol-based antioxidant: ADEKA AO-60) were mixed under nitrogen using a Three-One Motor manufactured by Shinto Chemical Co., Ltd. at 150°C for 3 hours. The mixture was then cooled to room temperature to prepare gel composition 7. The viscosity and thickening effect of the obtained gel composition 7 were measured according to the above-mentioned methods. The results are shown in Example 4 of Table 2.

[0118] <Examples 5 to 6: Suitable as cosmetic gel compositions, Comparative Examples 4 and 7> Gel compositions 8 to 10 and 16 were produced in the same manner as in Example 4, except that the hydrogenated block copolymer (SEEP-1) produced in Production Example 1 was replaced with the hydrogenated block copolymer (SEEP-2, SEEP-3, SEP-1, or SEEP-4) produced in Production Examples 2 to 4 and 7. The viscosity and thickening effect of the resulting gel compositions 8 to 10 and 16 were measured according to the methods described above. The results are shown in Table 2 for Examples 5 to 6 and Comparative Examples 4 and 7.

[0119] [Table 2] From Table 2, we can see the following: The gel compositions of Examples 4 to 6 had higher viscosities than the gel compositions of Comparative Examples 4 and 7. That is, SEEP-1, SEEP-2, and SEEP-3 had a higher thickening effect than SEEP-1 and SEEP-4.

[0120] Example 7: Suitable as a gel composition for lubricating oil 0.87 parts by mass of the hydrogenated block copolymer (SEEP-1) produced in Production Example 1, a kinematic viscosity at 40°C of 31 mm 2 99.13 parts by mass of a base oil having a viscosity of 1 / s (component ratio: paraffin 67 (% Cp), naphthene 27 (% Cn), aroma 6 (% Ca); viscosity index: 106; hue: yellow) and 0.05 parts by mass of an antioxidant (hindered phenol antioxidant: ADEKA AO-60) were mixed under nitrogen at 150°C for 3 hours using a Three-One Motor manufactured by Shinto Chemical Co., Ltd. The mixture was then cooled to room temperature to prepare gel composition 11. The kinematic viscosity and viscosity index of the obtained gel composition 11 at 40° C. and 100° C. were measured according to the above-mentioned method. The results are shown in Table 3 for Example 7.

[0121] <Examples 8 to 9: Suitable as a gel composition for lubricating oil, Comparative Examples 5 and 8> The hydrogenated block copolymer (SEEP-1) produced in Production Example 1 was replaced with the hydrogenated block copolymer (SEEP-2, SEEP-3, SEEP-1, or SEEP-4) produced in Production Examples 2 to 4 and 7, and the kinematic viscosity at 100°C was about 10 mmHg as shown in Table 3 below. 2 Gel compositions 12 to 14 and 17 were produced in the same manner as in Example 7, except that the content of the hydrogenated block copolymer was changed so that the kinematic viscosity was 1 / s. The kinematic viscosity and viscosity index of the resulting gel compositions 12 to 14 and 17 at 40°C and 100°C were measured according to the methods described above. The results are shown in Table 3 for Examples 8 to 9 and Comparative Examples 5 and 8.

[0122] [Table 3] The following can be seen from Table 3. The gel compositions of Examples 7 to 9 had a lower content of hydrogenated block copolymer than the gel compositions of Comparative Examples 5 and 8, although they had equivalent kinematic viscosities and viscosity indexes at 100°C. That is, SEEP-1, SEEP-2, and SEEP-3 had a higher thickening effect than SEEP-1 and SEEP-4.

[0123] Example 10: Suitable as a gel composition for grease 10 parts by mass of the hydrogenated block copolymer (SEEP-1) produced in Production Example 1 and 90 parts by mass of base oil were mixed under nitrogen for 2 hours at 150°C using a Three-One Motor manufactured by Shinto Chemical Co., Ltd. The mixture was then cooled to room temperature to prepare a copolymer composition. 20 parts by mass of the obtained copolymer composition and 80 parts by mass of lithium grease were mixed with a stainless steel spatula for 30 minutes at 80 to 90° C. Thereafter, the mixture was cooled to room temperature to prepare gel composition 18. The mixed consistency, mixed stability, consistency increase, oil separation, and water wash resistance of the obtained gel composition 18 were measured according to the above-mentioned methods. The results are shown in Example 10 of Table 4.

[0124] Example 11: Suitable as a Gel Composition for Grease, Comparative Examples 9 to 11 In Example 11, the hydrogenated block copolymer (SEEP-1) produced in Production Example 1 was used, and in Comparative Examples 9 to 11, the hydrogenated block copolymer (SEEP-1) produced in Production Example 1 was replaced with the hydrogenated block copolymer (SEP-1 or SEEP-4) produced in Production Examples 4 and 7, respectively. Gel compositions 19 to 22 were produced in the same manner as in Example 10, except that the base oil content and the hydrogenated block copolymer content were changed as shown in Table 4 below. The resulting gel compositions 19 to 22 were measured for their mixed consistency, mixed stability, consistency increase, oil separation, and water wash resistance according to the methods described above. The results are shown in Table 4 for Example 11 and Comparative Examples 9 to 11.

[0125] [Table 4]

[0126] (Note 1) MonotaRO Corporation, "Otokomae MonotaRO (registered trademark) Lithium Grease" (consistency number: No. 2, thickener: lithium soap, thickener content: 10% by mass, base oil: mineral oil, base oil content: 85 to 90% by mass) (Note 2) "Samic (registered trademark) G-150" (Group II mineral oil) manufactured by Sanwa Chemical Industry Co., Ltd.

[0127] The following can be seen from Table 4. The gel compositions of Examples 10 and 11 have comparable water wash resistance compared to the gel compositions of Comparative Examples 9 to 11, but have a lower blend consistency (higher thickening effect), a smaller difference between blend consistency and blend stability (consistency increase) (higher shear stability), and a lower oil separation rate (higher oil retention). That is, compared to SEP-1 and SEEP-4, SEEP-1 exhibits the effect of being able to obtain a gel composition with a lower blend consistency (higher thickening effect), a smaller difference between blend consistency and blend stability (consistency increase) (higher shear stability), and a lower oil separation rate (higher oil retention). Example 10 was compared to Comparative Examples 9 and 11, and Example 11 was compared to Comparative Example 10. [Industrial Applicability]

[0128] The hydrogenated block copolymer of the present invention is useful as a cable filler for cables such as optical fiber cables, cosmetics, lubricating oils, and materials for gel compositions such as greases.

Claims

1. A hydrogenated block copolymer (a) is a hydrogenated product of a diblock copolymer having one polymer block (A) mainly composed of aromatic vinyl compound units and one polymer block (B) mainly composed of butadiene units (Bd) and isoprene units (Ip), the weight average molecular weight of the hydrogenated block copolymer (a) is 90,000 to 300,000; A hydrogenated block copolymer that satisfies the following requirements (I) and (II): (I) The following formula (i) is satisfied: α×β>6.500×10 ９ ・・・(i) (In formula (i), α represents the weight average molecular weight of the polymer block (A), and β represents the weight average molecular weight of the hydrogenated block copolymer (a).) (II) The degree of vinylation of the polymer block (B) is less than 35%.

2. 2. The hydrogenated block copolymer according to claim 1, wherein the content of the polymer block (A) in the hydrogenated block copolymer (a) is 40% by mass or less.

3. 2. The hydrogenated block copolymer according to claim 1, wherein the molar ratio of butadiene units (Bd) to isoprene units (Ip) in the polymer block (B) is Bd:Ip=25:75 to 75:

25.

4. The hydrogenated block copolymer according to claim 1, wherein the weight average molecular weight of the hydrogenated block copolymer (a) is 90,000 to 250,000.

5. The hydrogenated block copolymer according to claim 1, wherein the hydrogenation rate of the polymer block (B) is 90.0 mol % or more.

6. A gel composition comprising the hydrogenated block copolymer (a) according to claim 1 and a base oil (b).

7. 7. The gel composition according to claim 6, wherein the viscosity index of the base oil (b) is 70 to 150.

8. A cable filler comprising the gel composition of claim 6 or 7.

9. A cable comprising the gel composition of claim 6 or 7.

10. The cable of claim 9, wherein the cable is a fiber optic cable.

11. A cosmetic comprising the gel composition according to claim 6 or 7.

12. A lubricating oil comprising the gel composition of claim 6 or 7.

13. A grease comprising the gel composition of claim 6 or 7.

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