Block copolymers or their hydrogenated derivatives, adhesive compositions, asphalt modifiers, and thermoplastic resin modifiers.

Abstract

To provide a block copolymer or a hydrogenated product thereof having improved processability and mechanical strength.SOLUTION: There is provided a block copolymer or a hydrogenation product thereof which has a polymer block A composed mainly of a vinyl aromatic monomer unit and a polymer block B composed mainly of a conjugated diene monomer unit and / or a polymer block C composed of the vinyl aromatic monomer unit and the conjugated diene monomer unit, a weight average molecular weight of 80000 to 500000, a molecular weight distribution (Mw / Mn)A of 1.5 to 2.2, where the molecular weight distribution (Mw / Mn)H of a high molecular weight component is 1.2 to 1.4 and the molecular weight distribution (Mw / Mn)L of a low molecular weight component is 1.0 to 1.1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to block copolymers or their hydrogenated products, adhesive compositions, asphalt modifiers, and thermoplastic resin modifiers. [Background technology]

[0002] Block copolymers, composed of vinyl aromatic monomer units and conjugated diene monomer units, possess elasticity at room temperature similar to vulcanized natural or synthetic rubber without vulcanization, and exhibit moldability similar to thermoplastic resins at high temperatures. Therefore, they are widely used in fields such as footwear, plastic modification, asphalt modification, adhesives, household products, packaging materials for home appliances and industrial parts, and toys. Furthermore, hydrogenated versions of these block copolymers exhibit excellent weather resistance and heat resistance, and are widely used in applications beyond those mentioned above, including automotive parts and medical devices.

[0003] A common challenge in many of these applications is improving the balance between processability and mechanical strength. To address this, blends of high and low molecular weight components or branched block copolymers are commonly used. In other words, attempts are being made to achieve a high degree of compatibility between processability and mechanical strength by adjusting the amounts of high and low molecular weight components. Patent Document 1 discloses a radial block copolymer using a polyfunctional coupling agent in an adhesive composition, with the aim of improving the balance between processability, peel adhesion, and shear adhesion failure temperature. Patent Document 2 discloses a block copolymer composition for asphalt modification in which low and high molecular weight components coexist, with the aim of improving the balance between processability and mechanical strength such as softening point, toughness, and tenacity. Patent Document 3 discloses a radial hydrogenated block copolymer using a polyfunctional coupling agent, with the aim of obtaining a thermoplastic elastomer composition with excellent fluidity, compression set, flexibility, and weather resistance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 4130983 [Patent Document 2] Patent No. 4069389 [Patent Document 3] Patent No. 5815239 [Overview of the project] [Problems that the invention aims to solve]

[0005] As described above, in various applications, attempts have been made to improve the balance between processability and mechanical strength of block copolymers or their hydrogenated products (hereinafter also simply referred to as block copolymers) consisting of vinyl aromatic monomer units and conjugated diene monomer units.

[0006] However, while the coexistence of low-molecular-weight and high-molecular-weight components has attracted attention, no block copolymers or their hydrogenated products exhibiting sufficient mechanical strength and processability are known, and it has become clear that further improvements in mechanical strength and processability can be expected.

[0007] Therefore, the object of the present invention is to provide a block copolymer with improved processability and mechanical strength. [Means for solving the problem]

[0008] The inventors of the present invention conducted diligent studies to solve the above problems and found that the above problems can be solved by using a block copolymer having a predetermined monomer unit, a predetermined weight-average molecular weight, and a predetermined molecular weight distribution, thereby completing the present invention.

[0009] In other words, the present invention is as follows: [1] Polymer block A, mainly composed of vinyl aromatic monomer units, It has a polymer block B mainly composed of conjugated diene monomer units and / or a polymer block C composed of vinyl aromatic monomer units and conjugated diene monomer units, The weight average molecular weight is 80,000 to 500,000, The molecular weight distribution (Mw / Mn) A is 1.5 to 2.2, The molecular weight distribution (Mw / Mn) of the high molecular weight component H is 1.2 to 1.4, The molecular weight distribution (Mw / Mn) of the low molecular weight component L is 1.0 to 1.1, The above high molecular weight component is a polymer component having a molecular weight above the reference molecular weight, The above low molecular weight component is a polymer component having a molecular weight below the reference molecular weight, The above reference molecular weight is the molecular weight at the bottom peak located on the lowest molecular weight side among the bottom peaks between molecular weight peak X and molecular weight peak Y, The above molecular weight peak X is the peak located on the lowest molecular weight side among the molecular weight peaks obtained by gel permeation chromatography and having a weight average molecular weight of 20,000 or more, Molecular weight peak Y is a molecular weight peak adjacent to the above molecular weight peak X and located on the higher molecular weight side thereof, A block copolymer or a hydrogenated product thereof. [2] The maximum peak molecular weight of the above high molecular weight component obtained by gel permeation chromatography is 2.5 to 4.0 times that of the maximum peak molecular weight of the above low molecular weight component, The above high molecular weight component contains a ultra-high molecular weight component having a molecular weight of 10 times or more the maximum peak molecular weight of the above low molecular weight component, The content of the above ultra-high molecular weight component is 1 to 10% by mass based on the total amount of the above block copolymer, The block copolymer or a hydrogenated product thereof according to [1]. [3] The maximum peak molecular weight of the above low molecular weight component is 30,000 to 200,000, The block copolymer or a hydrogenated product thereof according to [1] or [2]. [4] The content of the above vinyl aromatic monomer units is 10 to 50% by mass relative to the total amount of the above block copolymer. Having a vinyl bond derived from the above-mentioned conjugated diene monomer unit, The amount of vinyl bonded is 5 to 90 mol% of the total amount of conjugated diene monomer units. [1] to [3] The block copolymer or hydrogenated thereof. [5] The content of the above vinyl aromatic monomer units is 10 to 50% by mass relative to the total amount of the above block copolymer. The amount of vinyl bond derived from the above-mentioned conjugated diene monomer units is 5 to 50 mol% of the total amount of the above-mentioned conjugated diene monomer units. The hydrogenation rate is 0 to 60 mol% relative to the total amount of unsaturated double bonds in the block copolymer before hydrogenation. The maximum peak molecular weight of the above low molecular weight components is between 30,000 and 100,000. [1] to [4] The block copolymer or hydrogenated thereof. [6] [5] The block copolymer or its hydrogenated form, 50 to 400 parts by mass of tackifier per 100 parts by mass of the above block copolymer, The above block copolymer contains 10 to 150 parts by mass of a softening agent per 100 parts by mass of the above block copolymer. Adhesive composition. [7] The content of the above vinyl aromatic monomer units is 20 to 50% by mass relative to the total amount of the above block copolymer. The amount of vinyl bond derived from the above-mentioned conjugated diene monomer units is 5 to 50 mol% of the total amount of the above-mentioned conjugated diene monomer units. The weight-average molecular weight of the above block copolymer is between 150,000 and 400,000. The maximum peak molecular weight of the above low molecular weight components is between 50,000 and 150,000. [1] to [4] The block copolymer or hydrogenated thereof. [8] The content of the block copolymer or its hydrogenated product described in [7] is 0.5 to 30% by mass relative to the total amount of asphalt. Composition for modifying asphalt. [9] The content of vinyl aromatic monomers is 10 to 65% by mass relative to the total amount of the block copolymer. The amount of vinyl bond derived from the above-mentioned conjugated diene monomer units is 30 to 90 mol% of the total amount of the above-mentioned conjugated diene monomer units. The hydrogenation rate is 80-100 mol% relative to the total amount of unsaturated double bonds in the block copolymer. The maximum peak molecular weight of the above low molecular weight components is between 50,000 and 200,000. [1] to [4] The block copolymer or hydrogenated thereof.

[10] [9] comprises the block copolymer or its hydrogenated form, 20 to 500 parts by mass of thermoplastic resin per 100 parts by mass of the above block copolymer, The above block copolymer contains 10 to 250 parts by mass of a softening agent per 100 parts by mass of the above block copolymer. A composition for modifying thermoplastic resins. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide block copolymers, adhesive compositions, asphalt compositions, and thermoplastic resin compositions that have good processability and improved mechanical strength by having predetermined monomer units, predetermined weight-average molecular weight, and predetermined molecular weight distribution. [Modes for carrying out the invention]

[0011] The block copolymer or its hydrogenated product of this embodiment comprises polymer block A mainly composed of vinyl aromatic monomer units, polymer block B mainly composed of conjugated diene monomer units, and / or polymer block C composed of vinyl aromatic monomer units and conjugated diene monomer units, and has a weight-average molecular weight of 80,000 to 500,000, with a molecular weight distribution (Mw / Mn) AThe ratio is 1.5 to 2.2, and the molecular weight distribution (Mw / Mn) of the high molecular weight component is H The ratio is 1.2 to 1.4, and the molecular weight distribution (Mw / Mn) of the low molecular weight component is L The molecular weight is 1.0 to 1.1, the high molecular weight component is a polymer component having a molecular weight equal to or greater than the reference molecular weight, the low molecular weight component is a polymer component having a molecular weight less than the reference molecular weight, the reference molecular weight is the molecular weight at the bottom peak located on the lowest molecular weight side among the bottom peaks between molecular weight peak X and molecular weight peak Y, molecular weight peak X is the peak located on the lowest molecular weight side among the molecular weight peaks with a weight-average molecular weight of 20,000 or more obtained in gel permeation chromatography, and molecular weight peak Y is the molecular weight peak adjacent to molecular weight peak X and located on its higher molecular weight side.

[0012] The term "vinyl aromatic monomer unit" refers to a structure corresponding to one vinyl aromatic hydrocarbon compound produced as a result of polymerizing vinyl aromatic hydrocarbon compounds.

[0013] Examples of vinyl aromatic hydrocarbon compounds include, but are not limited to, alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-tert-butylstyrene; alkoxystyrenes such as p-methoxystyrene; and vinylnaphthalene. Among these, styrene is preferred as the vinyl aromatic hydrocarbon. The vinyl aromatic hydrocarbon compound may be used alone or in combination of two or more.

[0014] A "conjugated diene monomer unit" refers to a structure that corresponds to one conjugated diene compound in the structure resulting from the polymerization of conjugated diene compounds.

[0015] The conjugated diene compound is not particularly limited as long as it is a diolefin having a conjugated double bond, but examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Among these, 1,3-butadiene and isoprene are preferred from the viewpoint of availability. Furthermore, 1,3-butadiene is more preferred because it tends to have excellent heat aging resistance and light resistance. The conjugated diene compound may be used alone or in combination of two or more.

[0016] (Block A) "Polymer block A mainly composed of vinyl aromatic monomer units" refers to a polymer block in which the mass ratio of vinyl aromatic monomer units to the total amount of polymer block A is greater than 90% by mass, and this mass ratio is preferably 95% by mass or more, and more preferably 98% by mass or more.

[0017] (Block B) "Polymer block B mainly composed of conjugated diene monomer units" refers to a polymer block in which the proportion of conjugated diene monomer units to the total amount of polymer block B is greater than 90% by mass, preferably 95% by mass or more, and more preferably 98% by mass or more.

[0018] (Block C) A polymer block C consisting of vinyl aromatic monomer units and conjugated diene monomer units is defined as a polymer block C containing only vinyl aromatic monomer units and conjugated diene monomer units, with a mass ratio of conjugated diene monomer units to vinyl aromatic monomer units in the range of 10:90 to 90:10. Furthermore, the vinyl aromatic monomer units in the copolymer block C may be uniformly distributed or tapered. In addition, multiple portions of the copolymer block C may contain vinyl aromatic monomer units uniformly distributed and / or tapered. Moreover, multiple portions of the copolymer block C may contain vinyl aromatic monomer units with different content.

[0019] Furthermore, the blocking rate of vinyl aromatic monomer units incorporated into the block copolymer can be determined using the following formula, obtained by oxidative decomposition of the block copolymer with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (as described in IMKOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)), using vinyl aromatic hydrocarbon polymer block components (however, vinyl aromatic hydrocarbon polymer components with an average degree of polymerization of approximately 30 or less are excluded). Blocking rate (by mass) of vinyl aromatic hydrocarbons = (Mass of vinyl aromatic monomer units in the block copolymer) / (Total amount of block copolymer)

[0020] The arrangement of polymer block A and polymer blocks B and / or C is not particularly limited, but from the viewpoint of fully exhibiting rubber elasticity as an elastomer, it is preferable that the molecule contains structures having multiple A blocks, such as linear structures ABA, ACA, BABA, BACA, ABCA, or coupling structures (AB-)nX, (AC-)nX, (BAB)nX, (BAC)nX.

[0021] In the above structure, each A independently represents polymer block A, each B independently represents polymer block B, and each C independently represents polymer block C. Each n is an independent integer greater than or equal to 2, and each X independently represents a residue of the coupling agent.

[0022] (Content of vinyl aromatic monomer units) The total amount of vinyl aromatic monomer units contained in the block copolymer of this embodiment is preferably 10 to 50% by mass. When the content of vinyl aromatic monomer units is within this range, the balance between mechanical strength and elongation tends to improve. Furthermore, from the viewpoint of the balance between flexibility, melt viscosity, holding power, and adhesive strength in the adhesive composition, an aromatic vinyl aromatic hydrocarbon content of 10 to 50% by mass is preferred. From the viewpoint of the balance between softening point and melt viscosity in the asphalt composition, 20 to 50% by mass is preferred. From the viewpoint of the balance between fluidity and compression set in the thermoplastic resin composition, 10 to 65% by mass is preferred.

[0023] The content of vinyl aromatic monomer units in the polymer composition is the block copolymer of this embodiment. This can be controlled by adjusting the amount of vinyl aromatic monomer added in the polymerization reaction. Furthermore, the content of vinyl aromatic monomer units in the polymer composition can be measured by the method described in the examples below.

[0024] (Amount of vinyl binding) The vinyl bond originates from the conjugated diene monomer units of the block copolymer in this embodiment. The microstructure of the conjugated diene portion in the block copolymer (ratio of cis, trans, and vinyl) can be controlled by using polar compounds, etc., as described later. When 1,3-butadiene is used as the conjugated diene, the amount of vinyl bond (mol%) relative to the total amount of conjugated diene monomer units is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, from the viewpoint of heat resistance and flexibility of the block copolymer; from the viewpoint of flexibility and heat resistance in adhesive compositions, a vinyl bond amount of 5 to 50 mol% is preferred; from the viewpoint of balance between softening point and melt viscosity in asphalt compositions, 5 to 50 mol% is preferred; and from the viewpoint of balance between fluidity and heat resistance in thermoplastic resin compositions, 30 to 90 mol% is preferred.

[0025] When isoprene is used as the conjugated diene, or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds shall be considered the amount of vinyl bonds. The amount of vinyl bonds can be measured by the method described in the examples below.

[0026] (Evaluation Criteria) The methods for evaluating the mechanical strength and processability of block copolymers or their hydrogenated products will be described in detail in the examples below, but mechanical strength can be indicated by tensile strength or compression set, and processability can be indicated by toluene solution viscosity (hereinafter also referred to as toluene viscosity or TV). In adhesive compositions, holding power or tackiness can be used as an indicator of mechanical strength, and 120°C melt viscosity can be used as an indicator of processability. In asphalt compositions using the block copolymer of this embodiment, the softening point can be used as an indicator of mechanical strength, and 180°C melt viscosity can be used as an indicator of processability. In thermoplastic resin compositions using the block copolymer of this embodiment, compression set can be used as an indicator of mechanical strength, and MFR can be used as an indicator of processability.

[0027] The preferred ranges for mechanical strength and processability vary depending on the application, and it is preferable to evaluate them based on the balance between mechanical strength and processability. In other words, generally, improving mechanical strength reduces processability, but it is preferable to evaluate them from the viewpoint of improving the balance between these two. Generally, when used as an adhesive composition, the tensile strength of the block copolymer or its hydrogenated product is preferably 5.5 MPa or higher, more preferably 6.5 MPa or higher, and the 15% TV is preferably 10 to 30 mPa·s. Furthermore, as an index representing the balance between mechanical strength and processability, it is preferable that the value of tensile strength / 15% TV is 0.30 or higher. Furthermore, when used as an asphalt composition, the tensile strength is preferably 10 MPa or higher, and the 5% TV is preferably 15 mPa·s or lower. As an indicator representing the balance between mechanical strength and workability, the value of tensile strength / 5% TV is preferably 1.50 or higher. Furthermore, when used as a thermoplastic resin composition, the compression set is preferably 28% or lower, more preferably 25% or lower, and the 5% TV is preferably 30 mPa·s or lower. As an indicator representing the balance between mechanical strength and workability, the value of compression set × 5% TV is preferably 800 or lower.

[0028] (Method of manufacturing block copolymers) The method for producing block copolymers is not particularly limited, but examples include the methods described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 51-49567, Japanese Patent Publication No. 59-166518, etc.

[0029] The solvent used in the production of block copolymers is not particularly limited, but examples include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; or hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene. These may be used individually or in combination of two or more.

[0030] The organolithium compounds used in the production of block copolymers are compounds having one or more lithium atoms bonded to the molecule, and are not particularly limited, but examples include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium, and the like.

[0031] For the purpose of adjusting the polymerization rate during the production of the block copolymer, changing the microstructure of the polymerized conjugated diene portion, adjusting the reactivity ratio of the conjugated diene and vinyl aromatic hydrocarbon, etc., polar compounds and randomizing agents can be used. The polar compounds and randomizing agents are not particularly limited, and examples thereof include ethers, amines, thioethers, phosphoramides, potassium salts or sodium salts of alkylbenzenesulfonic acids, alkoxides of potassium or sodium, and the like. Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, ditetrahydrofurylpropane (DTHFP), and ethyltetrahydrofurfuryl ether. As amines, tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can also be used. Examples of phosphine and phosphoramide include triphenylphosphine, hexamethylphosphoramide, and the like.

[0032] The polymerization temperature when producing the block copolymer is preferably -10 to 150 °C, more preferably 30 to 120 °C. The time required for polymerization varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 to 10 hours. Also, the atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure may be within a range sufficient to maintain the monomers and solvent in the liquid phase within the above polymerization temperature range, and is not particularly limited. Further, it is preferable to prevent impurities such as water, oxygen, and carbon dioxide gas, which inactivate the catalyst and living polymer, from mixing into the polymerization system.

[0033] (Molecular weight distribution) The block copolymer of this embodiment has a molecular weight distribution (Mw / Mn) A of 1.5 to 2.2, and the molecular weight distribution (Mw / Mn) of the high molecular weight component H is 1.2 to 1.4, and the molecular weight distribution (Mw / Mn) of the low molecular weight component L is 1.0 to 1.1.

[0034] Here, high molecular weight components are polymer components having a molecular weight equal to or greater than the reference molecular weight, low molecular weight components are polymer components having a molecular weight less than the reference molecular weight, the reference molecular weight is the molecular weight at the bottom peak located on the lowest molecular weight side among the bottom peaks between molecular weight peak X and molecular weight peak Y, molecular weight peak X is the peak located on the lowest molecular weight side among the molecular weight peaks with a weight-average molecular weight of 20,000 or more obtained in gel permeation chromatography, and molecular weight peak Y is the molecular weight peak adjacent to molecular weight peak X and located on its higher molecular weight side.

[0035] As described above, the molecular weight peaks (hereinafter also referred to as peak tops) of the block copolymer in this embodiment mean that there are at least two peaks with a molecular weight of 20,000 or more. In the region with a molecular weight of less than 20,000, peaks of polymer chains that were deactivated before multiple blocks were formed may appear. In addition to the presence of peaks of polymer chains in the region with a molecular weight of less than 20,000, the presence of multiple peak tops in the region of 20,000 or more means that the copolymer component having multiple blocks includes both low molecular weight and high molecular weight compounds.

[0036] Multiple peaks may be present in both the low-molecular-weight and high-molecular-weight components. For example, trace deactivated components with a molecular weight less than 20,000, generated by deactivation during the polymerization reaction, are included in the low-molecular-weight components, while multiple peaks originating from multiple branched structures obtained by using polyfunctional coupling agents or multiple coupling agents are all included in the high-molecular-weight components. When the block copolymer has a coupling structure, it is preferable to set the molecular weight such that the uncoupled portion forms the peak top of the low-molecular-weight component and the coupled portion forms the peak top of the high-molecular-weight component.

[0037] Molecular weight distribution of low molecular weight components (hereinafter, (Mw / Mn)) LAlso known as (Mw / Mn), sharpening the peak shape tends to increase the mechanical strength of the polymer. In the case of coupling structures, if there are many impurities in the polymerization raw materials, if there is a lot of deactivation during polymerization, or if deactivation is intentionally caused during polymerization, or if the initiator is added in segments, (Mw / Mn) L Considering that the ratio can exceed 1.1, it is recommended to reduce the amount of impurities and add the polymerization initiator all at once (Mw / Mn). L This is a preferred embodiment as it makes it easier to reduce the ratio to 1.1 or less. Furthermore, the molecular weight distribution of the high molecular weight component corresponding to the coupling product of the block copolymer (hereinafter, (Mw / Mn) H Also known as (Mw / Mn), this is adjusted to 1.2-1.4. H By setting it to 1.2 or higher, the polymer as a whole tends to exhibit sufficient mechanical strength, (Mw / Mn) H By keeping the value below 1.4, good machinability can be ensured, thus achieving a balance between strength and machinability.

[0038] As will be discussed later, when using commonly used coupling agents individually or in combination, (Mw / Mn) H Since it will not exceed 1.2, it is preferable to use a coupling agent that has a distribution in the number of branches (for example, a range of 4 or more functional groups) to give a range in the number of branches of the coupling product. Furthermore, (Mw / Mn) A This is adjusted to 1.5-2.2 (Mw / Mn). A (Mw / Mn) L (Mw / Mn) H This is determined by the weight ratio of high molecular weight components to low molecular weight components. The weight ratio of high molecular weight components to low molecular weight components can be adjusted arbitrarily, preferably 10:90 to 90:10. By adjusting to this ratio, the desired (Mw / Mn) A This makes it possible to achieve a high level of balance between mechanical strength and machinability.

[0039] Also, preferably (Mw / Mn) H (Mw / Mn) LThe difference is 0.11 or more, more preferably 0.12 or more, and even more preferably 0.15 or more. In other words, it is preferable that the high molecular weight component is sufficiently broad compared to the low molecular weight component. Furthermore, it is preferable that the block copolymer obtained in the present invention contains 1 to 10% by mass of the entire block copolymer, in which the maximum peak molecular weight of the high molecular weight component is in the range of 2.5 to 4.0 times the maximum peak molecular weight of the low molecular weight component (hereinafter this ratio is also called the jump rate), and the ultra-high molecular weight component has a molecular weight of 10 times or more the maximum peak molecular weight of the low molecular weight component. The lower limit of the ultra-high molecular weight component is more preferably 1.5% by mass or more of the entire block copolymer, even more preferably 2.0% by mass or more, and particularly preferably 2.5% by mass or more. In other words, even though the main component of the high molecular weight component is relatively low molecular weight, by including a certain amount of the ultra-high molecular weight component, when used as a viscous adhesive composition, low viscosity and high retention or high adhesive strength can be achieved, and when used as an asphalt resin, low viscosity and a high softening point can be achieved. Furthermore, when used as a thermoplastic resin composition, low viscosity and low compression set can be achieved. In other words, the shape of the molecular weight distribution curve is preferably one that has a tail on the ultra-high molecular weight side.

[0040] Furthermore, in addition to having a controlled molecular weight distribution, the weight-average molecular weight (hereinafter also simply referred to as Mw) of the entire block copolymer is in the range of 80,000 to 500,000, making it possible to achieve a high degree of balance between processability and mechanical strength within a practically usable range. In particular, from the viewpoint of balancing melt viscosity, holding power, or adhesive strength in adhesive compositions, the Mw of the entire block copolymer is preferably in the range of 80,000 to 200,000, and from the viewpoint of balancing melt viscosity and softening point in asphalt modification applications, the Mw of the entire block copolymer is preferably in the range of 150,000 to 400,000.

[0041] Furthermore, from the viewpoint of ease of production, the maximum peak molecular weight of the low molecular weight component of the block copolymer obtained in the present invention is preferably in the range of 30,000 to 200,000. From the viewpoint of the balance between melt viscosity and holding power in adhesive compositions, it is preferably in the range of 30,000 to 100,000. From the viewpoint of the balance between melt viscosity and softening point in asphalt modification applications, it is preferably in the range of 50,000 to 150,000. In addition, from the viewpoint of the balance between fluidity and compression set in thermoplastic resin compositions, it is preferably in the range of 50,000 to 200,000.

[0042] While there are no particular limitations on the method for obtaining block copolymers having these molecular weight distributions, it is preferable to add a coupling agent to the polymerization ends of living anionic polymerization to obtain high molecular weight and low molecular weight components simultaneously. By adopting a coupling structure, the microstructures of the low molecular weight and high molecular weight components become equivalent, making it less likely for differences in compatibility to occur between the low molecular weight and high molecular weight components when mixed with other resins or asphalt, improving uniformity and preventing a decrease in mechanical strength when the composition is formed. In other words, although it is possible to obtain the molecular weight distribution of the present invention by blending multiple types of polymers, the coupling structure is more preferable. More specifically, the difference in vinyl aromatic hydrocarbon content between the high molecular weight and low molecular weight components is preferably within 3% by mass, and more preferably within 1% by mass. Similarly, the amount of vinyl bonding is also preferably within 3% by mass, and more preferably within 1% by mass.

[0043] The coupling agent is not particularly limited, but from the viewpoint of stably obtaining the above molecular weight distribution, it is preferable that the coupling agent contains divinylbenzene as a constituent unit. More specifically, it is a polymer of divinylbenzene having multiple vinyl groups in the molecule. Furthermore, the coupling agent may optionally be copolymerized with other monomers such as conjugated dienes or vinyl aromatic hydrocarbons, and any functional group may be introduced. The divinylbenzene polymer preferably has an average number of vinyl groups in the molecule of 3 or more, and more preferably 5 or more. Here, the average vinyl group number refers to the average number of reactive vinyl bonds in 1 mole of coupling agent, specifically the number of residual vinyl groups derived from divinylbenzene expressed in moles. This can be quantified using nuclear magnetic resonance (NMR) spectroscopy.

[0044] The average number of vinyl groups is the average value of the number of residual vinyl groups in the coupling agent, meaning that the number of vinyl groups itself has a distribution. For example, a mixture of divinylbenzene polymers with approximately 1 to 10 vinyl groups, where the average number of vinyl groups is 3 or more or 5 or more, is one preferred embodiment of the coupling agent from the viewpoint of broadening the molecular weight distribution of high molecular weight components. The coupling agent itself also has a broad molecular weight distribution, and specifically, it is preferable that Mw / Mn is in the range of 1.3 to 5.0.

[0045] The coupling agent may be prepared and used by those skilled in the art. The method for preparing the coupling agent is not particularly limited, but it can be easily obtained, for example, by deactivating an anionic polymerization initiator prepared with reference to Japanese Patent Application Publication No. 10-158315 using methanol or the like.

[0046] Thus, by using a pre-prepared coupling agent, it is possible not only to obtain the desired molecular weight distribution with good reproducibility, but also to suppress the formation of gel components. When divinylbenzene is simply used as a coupling agent, it is difficult to control the crosslinking reaction between divinylbenzenes during the coupling reaction, making it difficult to reproduce the molecular weight distribution curve. Furthermore, the jump rate increases, often generating gel components that are insoluble in the solvent. On the other hand, by using 2- to 4-functional alkoxysilane compounds or halogen compounds such as silicon tetrachloride, which are commonly used as coupling agents, coupling structures mainly consisting of 3-branched or 4-branched components can be obtained, and these can also be used in any combination. However, when the inventors investigated the molecular weight distribution of high molecular weight components in embodiments where coupling agents with 2- to 4 functional groups were used, the molecular weight distribution of high molecular weight components in the resulting block copolymer was less than 1.2, and the overall molecular weight distribution was 1.1-1.5, making it difficult to obtain the desired molecular weight distribution. In other words, it is not possible to achieve both high processability and mechanical strength simultaneously. If the molecular weight distribution of the uncoupled portion is broadened by, for example, partial addition of polymerization initiator, the distribution of high molecular weight components on the coupling side will also broaden, but in that case, the distribution of low molecular weight components will no longer be satisfied. Furthermore, when using multiple coupling agents in combination, a realistic number of 2 to 4 is insufficient to obtain the desired molecular weight distribution. In addition, this approach is undesirable from the standpoint of the complexity of controlling the reaction, the resulting decrease in production efficiency, and the reproducibility of the molecular weight distribution curve.

[0047] The block copolymer may be hydrogenated (hereinafter simply referred to as hydrogenation) with respect to the unsaturated double bonds in the block copolymer. The hydrogenation catalyst is not particularly limited, and for example, conventionally known hydrogenation catalysts include (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc., (2) so-called Ziegler-type hydrogenation catalysts using organic acid salts of Ni, Co, Fe, Cr, etc. or transition metal salts such as acetylacetone salts and reducing agents such as organoaluminum, and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, and Zr. Specific hydrogenation catalysts that can be used include those described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041. Preferred hydrogenation catalysts include mixtures of titanocene compounds and / or reducing organometallic compounds.

[0048] As titanocene compounds, compounds described in Japanese Patent Publication No. 8-109219 can be used, but specific examples include compounds having at least one ligand with a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. As reducing organometallic compounds, examples include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, or organozinc compounds.

[0049] The hydrogenation reaction is preferably carried out in a temperature range of 0 to 200°C, more preferably 30 to 150°C. The hydrogen pressure used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction can be used as a batch process, a continuous process, or a combination thereof.

[0050] When a block copolymer is its hydrogenated product, the total hydrogenation rate of the unsaturated double bonds based on the conjugated diene compound (hereinafter also referred to as the hydrogenation rate) can be arbitrarily selected according to the purpose and is not particularly limited. For example, when heat resistance is required during processing, molding, or use, the hydrogenation rate of the unsaturated double bonds based on the conjugated diene compound in the block copolymer is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. In addition, only a portion may be hydrogenated for purposes such as controlling compatibility with other resins or controlling the crosslinking rate. When only a portion is hydrogenated, it is recommended that the hydrogenation rate be 10 mol% or more and less than 70 mol%, or 15 mol% or more and less than 65 mol%, and optionally 20 mol% or more and less than 60 mol%. Furthermore, in hydrogenated block copolymers, it is recommended that the hydrogenation rate of the vinyl bonds based on the conjugated diene before hydrogenation be preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more, in order to obtain a resin composition with excellent thermal stability.

[0051] In adhesive compositions, the hydrogenation rate is preferably in the range of 0 to 60 mol% from the viewpoint of compatibility with the tackifying resin and heat resistance, and in thermoplastic resin compositions, it is preferably in the range of 80 to 100 mol% from the viewpoint of compression set, heat resistance and weather resistance.

[0052] Here, the hydrogenation rate of vinyl bonds refers to the proportion of hydrogenated vinyl bonds among the vinyl bonds based on the conjugated diene before hydrogenation incorporated into the block copolymer. The hydrogenation rate can be adjusted by changing the amount of hydrogen added to the block copolymer. There are no particular restrictions on the hydrogenation rate of the aromatic double bonds based on vinyl aromatic hydrocarbons in the block copolymer, but it is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. The hydrogenation rate can be determined by nuclear magnetic resonance (NMR) spectroscopy.

[0053] The block copolymer or its hydrogenated product obtained as described above can be separated from the solution by removing catalyst residue as needed. Methods for separating the solvent include, for example, adding a polar solvent that is a poor solvent for the polymer, such as acetone or alcohol, to the solution after polymerization or hydrogenation to precipitate and recover the polymer; adding the polymer solution to hot water under stirring and removing the solvent by steam stripping; or directly heating the polymer solution to remove the solvent by distillation. In addition, various stabilizers such as phenolic stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the block copolymer or its hydrogenated product in this invention.

[0054] (Adhesive composition) The adhesive composition of this embodiment preferably contains the block polymer of this embodiment described above, 50 to 400 parts by mass of a tackifier and 10 to 150 parts by mass of a softener per 100 parts by mass of the block polymer. This provides an excellent balance between adhesive properties and melt viscosity in the adhesive composition of this embodiment.

[0055] The content of the tackifier is preferably 100 to 380 parts by mass, and more preferably 150 to 350 parts by mass, per 100 parts by mass of the block polymer of this embodiment. The content of the softener is preferably 30 to 130 parts by mass, and more preferably 70 to 120 parts by mass, per 100 parts by mass of the block polymer.

[0056] The ratio of the content of each of the above components can be arbitrarily changed by adjusting the amount of each component used in the adhesive composition.

[0057] Here, the block copolymer used in the adhesive composition preferably has a content of 10 to 50% by mass of vinyl aromatic monomer units relative to the total amount of the block copolymer, a vinyl bond amount derived from the conjugated diene monomer units of 5 to 50 mol% relative to the total amount of the conjugated diene monomer units, a hydrogenation rate of 0 to 60 mol% relative to the total amount of unsaturated double bonds in the block copolymer, and a maximum peak molecular weight of 30,000 to 100,000 for the low molecular weight component.

[0058] Furthermore, the same methods as described above can be used to adjust the content of vinyl aromatic monomer units, the amount of vinyl bonds derived from conjugated diene monomer units, the hydrogenation rate, and the weight-average molecular weight of low molecular weight components.

[0059] (Adhesion-enhancing agent) Tackifiers can be selected from a wide variety of types depending on the application and required performance of the resulting adhesive composition. Examples of tackifiers, but not limited to the following, include natural rosin, modified rosin, hydrogenated rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, pentaerythritol ester of hydrogenated rosin, copolymers of natural terpenes, three-dimensional polymers of natural terpenes, hydrogenated derivatives of hydrogenated terpene copolymers, polyterpene resins, hydrogenated derivatives of phenolic modified terpene resins, aliphatic petroleum hydrocarbon resins, hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins. These tackifiers can be used individually or in combination of two or more types.

[0060] The tackifier is colorless to pale yellow, virtually odorless, and has good thermal stability. In that case, liquid-type tackifying resins can also be used. Other tackifying agents besides hydrogenated derivatives include, but are not limited to, aliphatic resins, alicyclic resins, polyterpenes, natural and modified rosin esters, and mixtures thereof. Specific examples include "Wingtack Extra" (trade name) from Sartomer, "Piccotac" (trade name) from Eastman Chemical Company, "Escorez" (trade name) from ExxonMobil Chemical Company, "Sylvagum" (trade name) and "Sylvalite" (trade name) from Arizona Chemical Company, and "Piccolyte" (trade name) from Ashland. Hydrogenated derivatives are preferred as tackifying resins in terms of difficulty in coloring and low odor. Among these, hydrogenated dicyclopentadiene resins are particularly preferred. Examples of such hydrogenated derivatives include, but are not limited to, Alcon P100 (trade name) and Alcon M115 (trade name) from Arakawa Chemical Corporation, Clearon P135 (trade name) from Yasuhara Chemical Co., Ltd., and ECR5400 (trade name) from Exxon Corporation. In the adhesive composition of this embodiment, if high adhesion, resistance to changes in adhesive strength over time, or creep performance are required, it is more preferable to contain in the adhesive composition 20 to 75% by mass of a tackifying resin that has affinity for the non-glass phase blocks (usually intermediate blocks) of the block copolymer, and 3 to 30% by mass of a tackifier that has affinity for the glass phase blocks (usually outer blocks) of the block polymer. As the tackifier that has affinity for the glass phase blocks, a tackifying resin for the terminal blocks is preferred. The tackifying resin is mainly an aromatic resin, and examples include homopolymers or copolymers containing vinyltoluene, styrene, α-methylstyrene, coumarone, or indene. Furthermore, among these, Kristalex and Plastalyn (manufactured by Eastman Chemical Corporation, trade name), which contain α-methylstyrene, are preferred. The content of the tackifier for the end block in the adhesive composition is preferably in the range of 3 to 30% by mass, more preferably in the range of 5 to 20% by mass, and even more preferably in the range of 6 to 12% by mass. When high initial adhesion, high wettability, low melt viscosity or high coating properties, and discharge stability of the adhesive composition are required, the tackifier used in the adhesive composition is preferably a petroleum resin with an aroma content of 3 to 12% by mass. An aroma content of 4 to 10% by mass is more preferable, and hydrogenated petroleum resin is particularly preferred.

[0061] (Softener) Examples of softeners include, but are not limited to, oils, plasticizers, liquid tackifiers (with a ring-spherical softening point lower than 30°C), synthetic liquid oligomers, and mixtures thereof. While not particularly limited, known paraffinic or naphthenic process oils and mixtures thereof can be used. Examples of commercially available products include, but are not particularly limited, Diana Fresia S32 (trade name), Diana Process Oil PW-90 (trade name), Process Oil NS100 (trade name) from Idemitsu Kosan Co., Ltd., White Oil Broom 350 (trade name), DN Oil KP-68 (trade name) from Kukdong Oil & Chem, Enerper M1930 (trade name) from BP Chemicals, Kaydol (trade name) from Crompton, Primol 352 (trade name) from Esso, and KN4010 (trade name) from PetroChina Company.

[0062] (Other ingredients) The adhesive composition of this embodiment may optionally contain other components depending on the purpose. Such other components are not particularly limited, but may include, for example, other polymers or stabilizers.

[0063] (Composition for modifying asphalt) In the asphalt modifying composition of this embodiment, from the viewpoint of high softening point properties, it is preferable that the block copolymer of this embodiment be contained in an amount of 0.5% by mass or more and 30% by mass or less relative to the total amount of asphalt, and from the viewpoint of the asphalt composition having an even higher softening point property, it is more preferable that it be 2% by mass or more, even more preferable that it be 3% by mass or more, and particularly preferable that it be 3.5% by mass or more. On the other hand, in the asphalt composition of this embodiment, from the viewpoint of the asphalt composition having an even lower melt viscosity, the content ratio of the block copolymer (P) is more preferable that it be 20% by mass or less, even more preferable that it be 16% by mass or less, and particularly preferable that it be 14% by mass or less.

[0064] The ratio of the content of each of the above components can be arbitrarily changed by adjusting the amount of each component used in the asphalt modifier composition.

[0065] Here, the block copolymer used in the asphalt modifier composition preferably has a vinyl aromatic monomer unit content of 20 to 50% by mass relative to the total amount of the block copolymer, a vinyl bond amount derived from conjugated diene monomer units of 5 to 50 mol% relative to the total amount of conjugated diene monomer units, a weight-average molecular weight of 150,000 to 400,000, and a maximum peak molecular weight of 50,000 to 150,000 for the low molecular weight component.

[0066] Furthermore, the same methods as described above can be used to adjust the content of vinyl aromatic monomer units, the amount of vinyl bonds derived from conjugated diene monomer units, and the weight-average molecular weight of the block copolymer.

[0067] (asphalt) The asphalt used in the asphalt modifying composition of this embodiment is not limited to the following, but examples include asphalt obtained as a by-product of petroleum refining (petroleum asphalt), or as a natural product (natural asphalt), or a mixture of these asphalts and petroleum products. Asphalt usually contains bitumen as its main component.

[0068] Examples of asphalt include, but are not limited to, straight asphalt, semi-blown asphalt, blown asphalt, solvent-de-pasteurized asphalt, cutback asphalt with added tar, pitch, or oil, and asphalt emulsion. Among these, straight asphalt is preferred from the standpoint of availability. These may be used individually or in mixtures.

[0069] Furthermore, various types of asphalt may be mixed with petroleum-based solvent extracts, aromatic hydrocarbon process oils, or aromatic heavy mineral oils such as extracts. The mixing method is not particularly limited, but can be carried out using any mixer, for example.

[0070] Mixers are not particularly limited, but examples include extruders, kneaders, melting and kneading machines such as Banbury mixers, agitators such as vertical impellers and side-arm impellers, homogenizers including emulsifiers, and pumps.

[0071] In the method for producing the asphalt composition of this embodiment, although not particularly limited, it is preferable to mix asphalt, block copolymer, crosslinking agent, and any additives in a stirring tank or the like at a temperature in the range of 140°C to 220°C.

[0072] (Other ingredients) The asphalt composition of this embodiment may optionally contain other components depending on the purpose, and is not particularly limited, but may contain, for example, various fillers, silane coupling agents, and stabilizers, and the asphalt composition may be vulcanized.

[0073] (Thermoplastic resin composition) The thermoplastic resin composition of this embodiment contains 20 to 500 parts by mass of thermoplastic resin and 10 to 250 parts by mass of a softener per 100 parts by mass of the block polymer of this embodiment described above. This provides an excellent balance of fluidity and compression set in the thermoplastic resin composition of this embodiment. The content of the thermoplastic resin is preferably 30 to 250 parts by mass, more preferably 50 to 230 parts by mass, per 100 parts by mass of the block polymer of this embodiment. The content of the softener is preferably 20 to 150 parts by mass, more preferably 30 to 120 parts by mass.

[0074] The ratio of the content of each of the above components can be arbitrarily changed by adjusting the amount of each component used in the thermoplastic resin composition.

[0075] Here, the block copolymer used in the thermoplastic resin composition is preferably a block copolymer in which the content of vinyl aromatic monomers is 10 to 65% by mass relative to the total amount of the block copolymer, the amount of vinyl bonds derived from the conjugated diene monomers is 30 to 90 mol% relative to the total amount of the conjugated diene monomers, the hydrogenation rate is 80 to 100% relative to the total amount of unsaturated double bonds in the block copolymer, and the weight-average molecular weight of the low molecular weight components is 50,000 to 200,000.

[0076] Furthermore, the same methods as described above can be used to adjust the content of vinyl aromatic monomers, the amount of vinyl bonds derived from the above-mentioned conjugated diene monomer units, the hydrogenation rate, and the weight-average molecular weight of the low molecular weight components.

[0077] (thermoplastic resin) The thermoplastic resin is not particularly limited, but examples include block copolymer resins of conjugated diene compounds and vinyl aromatic compounds, polymers of vinyl aromatic compounds, copolymer resins of vinyl aromatic compounds and other vinyl monomers such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, etc., rubber-modified styrene resins (HIPS), acrylonitrile-butadiene-styrene copolymer resins (ABS), methacrylate ester-butadiene-styrene copolymer resins (MBS), olefin polymers, cyclic olefin resins such as ethylene-norbornene resin, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins, polymers of acrylic acid and its esters and amides, polyacrylate resins, polymers of acrylonitrile and / or methacrylonitrile, and these Examples of copolymers of crironitrile monomers with other copolymerizable monomers containing 50% by mass or more include nitrile resins, polyamide resins, polyester resins, thermoplastic polyurethane resins, polycarbonate resins, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, polyoxymethylene resins, polyphenylene ether resins, polyphenylene sulfide resins, polyarylate resins, polyketone resins, fluorine resins, polyurethane resins, polyimide resins, and polybutadiene resins. These thermoplastic resins can be used individually or in combination of two or more. Among these, olefin polymers such as polypropylene and polyethylene are preferred.

[0078] (Softener) The softener incorporated into the thermoplastic resin composition is not particularly limited, but for example, known paraffinic or naphthenic process oils and mixtures thereof can be used. Such commercially available products are not particularly limited, but examples include Diana Fresia S32 (trade name), Diana Process Oil PW-90 (trade name), Process Oil NS100 (trade name) from Idemitsu Kosan Co., Ltd., White Oil Broom 350 (trade name), DN Oil KP-68 (trade name) from Kukdong Oil & Chem, Enerper M1930 (trade name) from BP Chemicals, Kaydol (trade name) from Crompton, Primol 352 (trade name) from Esso, and KN4010 (trade name) from PetroChina Company.

[0079] (Other ingredients) The thermoplastic resin composition of this embodiment may optionally contain other components depending on the purpose. For example, it may contain various fillers and stabilizers, and the thermoplastic resin composition may be crosslinked. [Examples]

[0080] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples.

[0081] 1. Characteristics of block copolymers or their hydrogenated products (1) Styrene content A certain amount of thermoplastic elastomer was dissolved in chloroform and measured using a UV spectrophotometer (Shimadzu Corporation, UV-2450). The content of vinyl aromatic monomer units (styrene) was calculated using a calibration curve based on the peak intensity at the absorption wavelength (262 nm) attributed to the vinyl aromatic compound component (styrene).

[0082] (2) Vinyl bonding amount and hydrogenation rate The measurements were taken using a nuclear magnetic resonance spectrometer (BRUKER, DPX-400).

[0083] (3) Molecular weight distribution curve, reference molecular weight, maximum peak molecular weight, jump rate, molecular weight distribution The chromatogram was measured using GPC (the instrument was a Tosoh HLC-8320GPC EcoSEC, and the attached RI detector was used. Three PLgel Column MiniMix-C columns were used. Tetrahydrofuran was used as the solvent, and the measurement conditions were: temperature 40°C, flow rate 0.4 mL / min, sample concentration 0.1 mass%, and injection volume 30 μL). The obtained chromatogram was used, and the curve drawn as the differential molecular weight distribution was defined as the molecular weight distribution curve using a calibration curve obtained from measurements of commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene). At this time, a straight line was drawn so that the Mw at both ends was 1000 and 10 million, and this was used as the baseline. The molecular weight distribution curve was vertically divided into low molecular weight and high molecular weight components by the lowest molecular weight peak between the lowest molecular weight peak (Mw ≥ 20,000) and the next highest molecular weight peak. In this case, the molecular weight of the bottom peak was used as the reference molecular weight. For each of the low molecular weight and high molecular weight components, the maximum peak molecular weight was set to PM. wL and PM wH , and the molecular weight distribution (Mw / Mn) respectively L and (Mw / Mn) H This was requested. Also, PM wL PM wH The ratio was defined as the jump rate. The jump rate was rounded to the second decimal place and expressed as a value with one decimal place. In addition, the molecular weight Mw and molecular weight distribution Mw / Mn were calculated for the molecular weight distribution curve before splitting. Each Mw / Mn was rounded to the third decimal place and expressed as a value with two decimal places.

[0084] (4) Content of ultra-high molecular weight components In the molecular weight distribution curve obtained by the method described above, PM wL The molecule was vertically divided at 10 times its molecular weight, and the components present at even higher molecular weights among the high molecular weight components were defined as ultra-high molecular weight components. The area ratio of the ultra-high molecular weight components to the total area of ​​the entire molecule was defined as the content of the ultra-high molecular weight components. The content of the ultra-high molecular weight components was rounded to the second decimal place and expressed as a value to the first decimal place.

[0085] (5) 15% toluene viscosity The viscosity of the block copolymer at 15% toluene was measured as an indicator of its processability. A lower value, i.e., lower viscosity, indicates better processability. The measurement was performed by thoroughly dissolving the block copolymer in toluene to a concentration of 15% by mass, and then measuring it in a Cannon-Fenske viscosity tube in a constant temperature bath controlled at 25°C.

[0086] (6) 5% toluene viscosity The viscosity of the block copolymer at 5% toluene was measured as an indicator of its processability. A lower value, i.e., lower viscosity, indicates better processability. The measurement was performed by thoroughly dissolving the block copolymer in toluene to a concentration of 5% by mass, and then measuring it in a Cannon-Fenske viscosity tube in a constant temperature bath controlled at 25°C.

[0087] (7) Tensile strength Tensile strength was measured as an indicator of the mechanical strength of the block copolymer. A higher value indicates superior mechanical strength. The measurement was performed according to the tensile test method of JIS K6251, and the strength at fracture was measured.

[0088] (8) Compression set The compression set was measured as an indicator of the strength of the block copolymer. A smaller value indicates superior mechanical strength of the block copolymer. The measurement was performed in accordance with the JIS K6301 compression set test, and the 70°C compression set of the block copolymer was determined as follows. A test specimen was prepared by punching out a 2mm thick press sheet of the block copolymer into a 29mm diameter circle and stacking six of them. The initial thickness of the six stacked specimens was measured at 23°C. The specimens were then compressed by 25% and left in a 70°C oven for 22 hours. After removing the specimens from the oven and releasing the compression, the remaining strain (70°C compression set) in the specimens after leaving them at 23°C for 30 minutes was calculated using the following formula. 70°C compression set = (t0 - t1) / (t0 × 0.25) × 100 t0: Initial thickness of the test specimen (mm) t1: Thickness of the test specimen (mm) after releasing compression and leaving it at 23°C for 30 minutes.

[0089] Here, tensile strength and the value obtained by dividing the tensile strength by the value of 15%TV (tensile strength / 15%TV) (MPa / mPa·s) can be used as indicators to evaluate the balance between mechanical strength and processability, which are characteristics of block copolymers or their hydrogenated products. Therefore, the balance between mechanical strength and processability (hereinafter also simply referred to as "balance") of block copolymers or their hydrogenated products was evaluated using the following evaluation criteria. The results are shown in Tables 1 and 2. [Evaluation Criteria] ○: The tensile strength is 5.5 MPa or higher, and the tensile strength / 15% TV is greater than 0.3 (MPa / mPa·s). ×: The tensile strength is less than 5.5 MPa, or the tensile strength / 15% TV is 0.3 (MPa / mPa·s) or less.

[0090] Furthermore, as an index for evaluating the balance between mechanical strength and processability, which are characteristics of block copolymers or their hydrogenated products, tensile strength and the value obtained by dividing tensile strength by 5% TV (tensile strength / 5% TV) (MPa / mPa·s) can be used instead of the above evaluation criteria. Therefore, the balance between mechanical strength and processability of block copolymers or their hydrogenated products was evaluated using the following evaluation criteria. The results are shown in Tables 1 and 2. [Evaluation Criteria] ○: The tensile strength is 5.5 MPa or higher, and the tensile strength / 5% TV is 1.5 (MPa / mPa·s) or higher. ×: The tensile strength is less than 5.5 MPa, or the tensile strength / 5% TV is less than 1.5 (MPa / mPa·s).

[0091] Furthermore, as an index for evaluating the balance between mechanical strength and processability, which are characteristics of block copolymers or their hydrogenated products, the value obtained by multiplying the compression set by 5% TV (compression set × 5% TV) (mPa·s·%) can be used instead of the above evaluation criteria. Therefore, the balance between mechanical strength and processability of block copolymers or their hydrogenated products was evaluated using the following evaluation criteria. The results are shown in Tables 1 and 2. [Evaluation Criteria] ○: The compression set × 5% TV is 800 (mPa·s·%) or less. ×: The compression set × 5% TV is greater than 800 (mPa·s·%).

[0092] 2. Characteristics of the adhesive composition (Preparation of adhesive composition) As shown in Table 3, each component of the raw materials was uniformly mixed and melt-kneaded in a pressurized kneader (model: DR0.5-3MB-E, Moriyama Co., Ltd.) at 180°C, 50 rpm, for 30 minutes to obtain a uniform hot-melt type adhesive composition.

[0093] (1) Melt viscosity The adhesive compositions prepared as described above were measured at 120°C or 140°C using a Brookfield viscometer (Brookfield DV-III). The smaller this value, that is, the lower the viscosity, the better the processability.

[0094] (Making adhesive tape) The adhesive composition prepared as described above was cooled to room temperature and dissolved in toluene to obtain a toluene solution. The obtained toluene solution was coated onto a polyester film (Toray Industries, Inc., Lumirror S10 (thickness 50 μm)) using an applicator, and then held at room temperature for 30 minutes, followed by 7 minutes in a 70°C oven to completely evaporate the toluene and produce an adhesive tape. The coating thickness was 50 μm (substrate thickness 50 μm).

[0095] (2) Holding power The fabricated adhesive tape was attached to a SUS plate (SUS304) with a contact area of ​​15 mm x 25 mm. Then, a 1 kg load was applied vertically to the adhesive tape at 40°C or 50°C, and the holding time until the tape slipped off was measured to evaluate the holding force. A higher value indicates better holding power. The results are shown in Table 3.

[0096] (3) Adhesive strength The prepared adhesive tape was formed to a width of 25 mm, attached to a SUS plate (SUS304), and the peeling force at 180° was measured at a peeling speed of 300 mm / min to evaluate the adhesive strength. A higher value indicates better adhesion. The results are shown in Table 3.

[0097] Here, as an index for evaluating the balance between mechanical strength and processability, which are characteristics of adhesive compositions, the value obtained by dividing the 40°C holding strength by the 120°C melt viscosity (40°C holding strength / 120°C melt viscosity) (min / Pa·s) can be used. Therefore, the balance between mechanical strength and processability of the adhesive composition was evaluated using the following evaluation criteria. The results are shown in Table 3. [Evaluation Criteria] ○: The holding strength at 40°C and the melt viscosity at 120°C are 65 (min / Pa·s) or higher. ×: The holding strength at 40°C and the melt viscosity at 120°C are less than 65 (min / Pa·s).

[0098] Furthermore, as an index for evaluating the balance between mechanical strength and processability, which are characteristics of adhesive compositions, the value obtained by dividing the 50°C holding strength by the 140°C melt viscosity (50°C holding strength / 140°C melt viscosity) (min / Pa·s) can be used instead of the evaluation criteria mentioned above. Therefore, the balance between mechanical strength and processability of the adhesive composition was evaluated using the following evaluation criteria. The results are shown in Table 3. [Evaluation Criteria] ○: The holding strength at 50°C and the melt viscosity at 140°C are 0.22 (min / Pa·s) or higher. ×: The holding strength at 50°C and the melt viscosity at 140°C are less than 0.22 (min / Pa·s).

[0099] 3. Characteristics of the asphalt composition (Preparation of asphalt composition) As shown in Table 4, 350g of asphalt (straight asphalt 60-80 (manufactured by Nippon Oil Corporation)) was placed in a 750mL metal can, and the metal can was thoroughly immersed in a 180°C oil bath. Next, small amounts of each block copolymer were added to the molten asphalt while stirring, so that each copolymer was present in a concentration of 4% or 10% by mass. After all the materials were fully added, the mixture was stirred at a rotation speed of 3000 rpm for 60 minutes to prepare the asphalt composition.

[0100] (Softening point of asphalt composition (ring and ball method)) The softening point of the asphalt composition prepared as described above was measured in accordance with JIS-K2207. The sample was filled into a standard ring, supported horizontally in a glycerin solution, and a 3.5g sphere was placed in the center of the sample. When the solution temperature was increased at a rate of 5°C / min, the temperature at which the sample touched the bottom plate of the ring base due to the weight of the sphere (softening point) was measured. A higher value indicates better results. The results are shown in Table 4.

[0101] (Melting viscosity of asphalt composition) The melt viscosity of the asphalt composition at 180°C was measured using a Brookfield viscometer. A lower value, i.e., lower viscosity, indicates better processability. The results are shown in Table 4.

[0102] Here, as indicators for evaluating the balance between mechanical strength and processability, which are characteristics of asphalt compositions, the 180°C melt viscosity (Pa·s) and the value obtained by dividing the softening point by the 180°C melt viscosity (softening point / 180°C melt viscosity) can be used. Therefore, the balance between mechanical strength and processability of the asphalt composition was evaluated using the following evaluation criteria. The results are shown in Table 4. [Evaluation Criteria] ○: Melt viscosity at 180°C is less than 400 (Pa·s) and softening point / 180°C melt viscosity is 0.30 (min / Pa·s) or higher, or melt viscosity at 180°C is 400 (Pa·s) or higher and softening point / 180°C melt viscosity is 0.11 (min / Pa·s) or higher. ×: Melt viscosity at 180°C is less than 400 and softening point / 180°C melt viscosity is less than 0.30 (min / Pa·s), or melt viscosity at 180°C is 400°C or higher and softening point / 180°C melt viscosity is less than 0.11 (min / Pa·s)

[0103] 3. Properties of Thermoplastic Resin Compositions (Preparation of thermoplastic resin compositions) Each component of the raw materials listed in Table 5 was uniformly mixed, and the mixture was melt-kneaded at a set temperature of 230°C using a twin-screw extruder (TEX-30αII, manufactured by Japan Steel Works, Ltd., cylinder bore 30 mm) to produce pellets of thermoplastic resin composition.

[0104] (1) MFR The MFR of thermoplastic resin compositions was measured in accordance with JIS K 7210 (230°C, 2160g load), and the MFR (g / 10min) was evaluated according to the following evaluation criteria. A higher value, i.e., lower viscosity, indicates better processability. The results are shown in Table 5.

[0105] (2) Compression set The compression set of thermoplastic resin compositions was measured in accordance with JIS K6301. A 6.3 mm thick pressed sheet was used as the test specimen. Measurements were taken at 70°C for 22 hours. A smaller value indicates better performance. The results are shown in Table 5.

[0106] Here, as an index for evaluating the balance between mechanical strength and processability, which are characteristics of thermoplastic resin compositions, the value obtained by dividing MFR by compression set (MFR / compression set) (g / (10min·%)) can be used. Therefore, the balance between mechanical strength and processability of thermoplastic resin compositions was evaluated using the following evaluation criteria. The results are shown in Table 5. [Evaluation Criteria] ○: The MFR (Mortem Fault Set) is 0.20 g / (10 min·%) or higher. ×: MFR (Compression Set) is less than 0.20 g / (10 min·%).

[0107] 4. Preparation of hydrogenation catalyst The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method. One liter of dried and purified cyclohexane was charged into a nitrogen-purged reaction vessel, and 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. An n-hexane solution containing 200 mmol of trimethylaluminum was then added while stirring thoroughly, and the reaction was carried out at room temperature for approximately 3 days.

[0108] 5. Preparation of coupling agent The coupling agent used in the coupling reaction was prepared by the following method. <Coupling agent 1> A stirring device with an internal volume of 10 L and a jacketed tank reactor were cleaned, dried, and nitrogen-purged, and the coupling agent was prepared according to the following procedure. As the first step, 1200 g of cyclohexane, 200 g of butadiene monomer, 79.3 g of divinylbenzene, and 22.5 g of tetrahydrofuran were added. In the second step, after adjusting the solution temperature in the container to 40°C, 26g of n-butyllithium was added, and the reaction was allowed to proceed for 60 minutes while maintaining the internal temperature at 75°C. In the third step, 0.9 moles of methanol were added per mole of n-butyllithium to obtain a cyclohexane solution containing coupling agent 1. A portion of the solution was allowed to dry, and the amount of vinyl groups derived from divinylbenzene in coupling agent 1 (average number of reactive vinyl bonds) was quantified by NMR. The average number of reactive vinyl bonds was 6.0.

[0109] <Coupling agent 2> A cyclohexane solution containing coupling agent 2 was obtained by preparing the solution using the same procedure as for coupling agent 1, except that the amount of divinylbenzene was changed to 50 g. The average number of reactive vinyl bonds was 5.2. <Coupling agent 3> A cyclohexane solution containing coupling agent 3 was obtained by preparing the solution using the same procedure as for coupling agent 1, except that the amount of divinylbenzene was changed to 30 g. The average number of reactive vinyl bonds was 4.1. <Coupling agent 4> A cyclohexane solution containing coupling agent 4 was obtained by preparing the same procedure as for coupling agent 1, except that the amount of divinylbenzene was changed to 120 g. The average number of reactive vinyl bonds was 8.4. <Coupling agent 5> A cyclohexane solution containing coupling agent 5 was obtained by preparing the solution using the same procedure as for coupling agent 1, except that the amount of divinylbenzene was changed to 20 g. The average number of reactive vinyl bonds was 2.4. <Coupling agent 6> A cyclohexane solution containing coupling agent 6 was obtained by preparing the solution using the same procedure as for coupling agent 1, except that the amount of divinylbenzene was changed to 150 g. The average number of reactive vinyl bonds was 10.5. <Coupling agents 7-11> Furthermore, the following coupling agents were used for coupling agents 7-11. Coupling agent 7: Dimethyldichlorosilane Coupling agent 8: Tetramethoxysilane Coupling agent 9: Silicon tetrachloride Coupling agent 10: Dimethyl phthalate Coupling agent 11: Divinylbenzene

[0110] 6. Preparation of block copolymers <Example 1: Preparation of Block Copolymer 1> A stirring device with an internal volume of 100 L and a jacketed tank reactor were cleaned, dried, and nitrogen-purged, and then batch polymerization was carried out to produce block copolymers as follows. As the first step, a cyclohexane solution containing 38 L of cyclohexane and 45.0 parts by mass of styrene monomer was added. In the second step, after adjusting the solution temperature in the container to 40°C, 0.20 parts by mass of n-butyllithium was added to 100 parts by mass of the total monomer, and polymerization was carried out for 30 minutes. In the third step, a cyclohexane solution containing 55.0 parts by mass of a conjugated diene monomer (butadiene monomer) was added, and polymerization was carried out for a further 60 minutes while adjusting the reaction temperature to 80°C. In the fourth step, a cyclohexane solution containing coupling agent 1 was added so that the molar ratio of coupling agent 1 to n-butyllithium was 0.06, and after stirring for 30 minutes, methanol was added at a rate of 0.9 moles per mole of n-butyllithium to obtain a cyclohexane solution containing styrene-butadiene block copolymer 1. In the fifth step, 0.25 parts by mass of the antioxidant (octadecyl-3-(3,5-dibutyl-t-butyl-4-hydroxyphenyl)propionate) was added to 100 parts by mass of block copolymer 1. After desolvation by stripping, moisture was removed using a hot air dryer to obtain block copolymer 1. The physical properties and characteristics of the obtained block copolymer 1 were measured using the method described above. The manufacturing conditions and measurement results are shown in Table 1.

[0111] <Examples 2-8, 11, 12: Preparation of block copolymers 2-8, 11, 12> The procedure was carried out in the same manner as in Example 1, except that the types and amounts of various additives were changed, to obtain block copolymers 2-8, 11, and 12. The manufacturing conditions and measurement results for each are shown in Table 1. Comparative Examples 1-9, 12: Preparation of block copolymers 17-25, 28 The procedure was carried out in the same manner as in Example 1, except that the types and amounts of various additives were changed, to obtain block copolymers 17-25 and 28. The manufacturing conditions and measurement results for each are shown in Table 2.

[0112] <Comparative Example 10: Preparation of Block Copolymer 26> A stirring device with an internal volume of 100 L and a jacketed tank reactor were cleaned, dried, and nitrogen-purged, and then batch polymerization was carried out to produce block copolymers as follows. As the first step, a cyclohexane solution containing 38 L of cyclohexane and 45.0 parts by mass of styrene monomer was added. In the second step, the solution temperature in the container was adjusted to 40°C, and then 0.06 parts by mass of n-butyllithium was added to 100 parts by mass of the total monomer, and polymerization was carried out for 15 minutes. At the 15-minute mark, an additional 0.08 parts by mass of n-butyllithium was added, and polymerization was carried out for another 30 minutes. In the third step, a cyclohexane solution containing 55.0 parts by mass of a conjugated diene monomer (butadiene monomer) was added, and polymerization was carried out for a further 60 minutes while adjusting the reaction temperature to 80°C. In the fourth step, a cyclohexane solution containing divinylbenzene was added so that the molar ratio of coupling agent 1 to total n-butyllithium was 0.20, and after stirring for 30 minutes, methanol was added at a rate of 0.9 moles per mole of total n-butyllithium to obtain a cyclohexane solution containing styrene-butadiene block copolymer 22. In the fifth step, 0.25 parts by mass of the antioxidant (octadecyl-3-(3,5-dibutyl-t-butyl-4-hydroxyphenyl)propionate) was added to 100 parts by mass of block copolymer 22. After desolvation by stripping, moisture was removed using a hot air dryer to obtain block copolymer 26. The physical properties and characteristics of the obtained block copolymer 26 were measured using the method described above. The manufacturing conditions and measurement results are shown in Table 2.

[0113] <Example 9: Preparation of Block Copolymer 9> A stirring device with an internal volume of 100 L and a jacketed tank reactor were cleaned, dried, and nitrogen-purged, and then batch polymerization was carried out to produce block copolymers as follows. In the first step, a cyclohexane solution containing 38 L of cyclohexane and 15.0 parts by mass of styrene monomer was added, and then 0.5 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter also referred to as "TMEDA") were added for every mole of n-butyllithium to be added in the second step. In the second step, after adjusting the solution temperature in the container to 40°C, 0.14 parts by mass of n-butyllithium was added to 100 parts by mass of the total monomer, and polymerization was carried out for 30 minutes. In the third step, a cyclohexane solution containing 85.0 parts by mass of a conjugated diene monomer (butadiene monomer) was added, and polymerization was carried out for a further 60 minutes while adjusting the reaction temperature to 80°C. In the fourth step, a cyclohexane solution containing coupling agent 1 was added so that the molar ratio of coupling agent 1 to n-butyllithium was 0.06, and after stirring for 30 minutes, methanol was added at a rate of 0.9 moles per mole of n-butyllithium to obtain a cyclohexane solution containing a styrene-butadiene block copolymer. In the fifth step, the obtained block polymer was continuously hydrogenated at 95°C using the hydrogenation catalyst prepared as described above to obtain a cyclohexane solution containing block copolymer 9. The catalyst amount was 50 ppm, the hydrogen pressure in the hydrogenation polymerizer was 0.95 MPa, and the average residence time was 120 minutes. After the reaction was complete, 0.25 parts by mass of the antioxidant (octadecyl-3-(3,5-dibutyl-t-butyl-4-hydroxyphenyl)propionate) was added to 100 parts by mass of the block copolymer. After desolvation by stripping, moisture was removed using a hot air dryer to obtain block copolymer 9. The physical properties and characteristics of the obtained block copolymer 9 were measured using the method described above. The manufacturing conditions and measurement results are shown in Table 1.

[0114] <Examples 10, 12, 13-16: Preparation of block copolymers 10, 12, 13-16> The procedure was carried out in the same manner as in Example 9, except that the types and amounts of various additives were changed, to obtain block copolymers 10, 12, and 13-16. The manufacturing conditions and measurement results for each are shown in Table 1.

[0115] <Comparative Examples 11, 13-15: Preparation of Block Copolymers 27, 29-31> The procedure was carried out in the same manner as in Example 9, except that the types and amounts of various additives were changed, to obtain block copolymers 27, 29-31. The manufacturing conditions and measurement results for each are shown in Table 2.

[0116] Examples 1-16 achieved the desired molecular weight distribution, and comparisons with comparative examples showed a significant improvement in the balance between 15% TV and tensile strength, or between 5% TV and compression set. Furthermore, as seen in Comparative Examples 4-9, simply using or combining general coupling agents did not yield the desired molecular weight distribution, and the balance between 15% TV and tensile strength was inferior compared to the examples. It was also confirmed that, as in Comparative Example 10, the tensile strength decreased significantly when (Mw / Mn)L exceeded 1.1 due to the partial addition of the initiator. Additionally, a comparison between Example 1 and Comparative Example 3 showed that the tensile strength decreased significantly in the region where the total molecular weight of the block copolymer was 80,000 or less, while a comparison between Example 13 and Comparative Example 15 showed that 5% TV increased significantly in the region where the total molecular weight of the block copolymer was 500,000 or more. In other words, it was shown that having a specific molecular weight and molecular weight distribution is important for achieving a high balance between processability and mechanical strength.

[0117] 7. Preparation of adhesive compositions, production of adhesive tapes, and evaluation of physical properties. As described above, adhesive compositions and adhesive tapes were prepared for Examples 17-26 and Comparative Examples 16 and 17 according to the formulations shown in Table 3. The results of the physical property evaluation are shown in Table 3.

[0118] Examples 17-25 confirm that the adhesive composition using the block copolymer of the present invention exhibits a good balance of holding power and melt viscosity. In particular, a comparison of Example 17 and Example 20 shows that the balance is further improved when the molecular weight of the low molecular weight component of the block copolymer is 30,000 or more. A comparison of Example 17 with Examples 21 and 22 shows that the balance is further improved when the jump ratio is in the range of 2.5-4.0 and the ultra-high molecular weight component is in the range of 1-10% by mass. Furthermore, a comparison of Example 17 with Example 24 and Example 25 with Example 26 shows that the balance is further improved when the styrene content is in the range of 10-50% by mass.

[0119] 8. Preparation and evaluation of the physical properties of the asphalt composition. As described above, asphalt compositions were prepared for Examples 27-30 and Comparative Examples 18-21 according to the formulations shown in Table 4. The results of the physical property evaluation are shown in Table 4.

[0120] From the comparison of Examples 27 and 29 with Comparative Examples 18 and 20, and from the comparison of Examples 28 and 30 with Comparative Examples 19 and 21, it can be confirmed that the asphalt composition using the block copolymer of the present invention exhibits a good balance between softening point and melt viscosity.

[0121] 9. Preparation and property evaluation of thermoplastic resin compositions As described above, thermoplastic resin compositions were prepared for Examples 31-34 and Comparative Examples 22 and 23 according to the formulations shown in Table 5. The results of the physical property evaluation are shown in Table 5. Examples 31-34 confirm that thermoplastic resin compositions using the block copolymer of the present invention exhibit a good balance between compression set and MFR. In particular, a comparison of Example 31 and Example 32 shows that the balance is further improved when the molecular weight of the low molecular weight component of the block copolymer is 200,000 or less, and a comparison of Example 31 with Examples 33 and 34 shows that the balance is further improved when the jump ratio is in the range of 2.5-4.0 and the ultra-high molecular weight component is in the range of 1-10% by mass.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] [Table 5]

[0127] (component) The following ingredients were used, as listed in Tables 1-5. • Coupling agent type 1: The prepared coupling agent 1 • Coupling agent type 2: The two coupling agents prepared above • Coupling agent type 3: The above-prepared coupling agent 3 • Coupling agent type 4: The above-prepared coupling agent 4 • Coupling agent type 5: Prepared coupling agent 5 • Coupling agent type 6: Prepared coupling agent 6 • Coupling agent 7: Dimethyldichlorosilane • Coupling agent 8: Tetramethoxysilane • Coupling agent type 9: Silicon tetrachloride • Coupling agent 10: Dimethyl phthalate • Coupling agent type 11: Divinylbenzene • TF1: Alcon M100 (manufactured by Arakawa Chemical Industries, Ltd.) • TF2: Quinton R100 (manufactured by Nippon Zeon Co., Ltd.) • OIL1: Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) • OIL2: Diana Process Oil NS-90 (Manufactured by Shell) • Straight asphalt 60-80 (manufactured by Shin Nippon Oil Co., Ltd., penetration degree 60-80) • PP: Propylene-based block copolymer (R-TPO) Q-100F (manufactured by Basell) • Oil: Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) [Industrial applicability]

[0128] By using the block copolymer or its hydrogenated product of the present invention, adhesives, asphalts, and thermoplastic resins with excellent processability and mechanical strength can be provided, making them highly effective industrially and widely applicable.

Claims

1. Polymer block A mainly composed of vinyl aromatic monomer units, The polymer comprises polymer block B mainly consisting of conjugated diene monomer units and / or polymer block C consisting of vinyl aromatic monomer units and conjugated diene monomer units. The weight-average molecular weight is between 80,000 and 500,000. Molecular weight distribution (Mw / Mn) A The range is 1.5 to 2.

2. Molecular weight distribution (Mw / Mn) of high molecular weight components H The values ​​are 1.2 to 1.

4. Molecular weight distribution of low molecular weight components (Mw / Mn) L The values ​​are between 1.0 and 1.

1. The aforementioned high molecular weight component is a polymer component having a molecular weight equal to or greater than the standard molecular weight. The aforementioned low molecular weight component is a polymer component having a molecular weight less than the standard molecular weight. The aforementioned reference molecular weight is the molecular weight at the bottom peak located on the lowest molecular weight side among the bottom peaks between molecular weight peak X and molecular weight peak Y. The molecular weight peak X is the lowest molecular weight peak among the molecular weight peaks obtained in gel permeation chromatography, where the weight-average molecular weight is 20,000 or more. Molecular weight peak Y is a molecular weight peak adjacent to molecular weight peak X, located on the higher molecular weight side. Block copolymer or its hydrogenated derivative.

2. The maximum peak molecular weight of the high molecular weight component obtained in gel permeation chromatography is 2.5 to 4.0 times that of the maximum peak molecular weight of the low molecular weight component. The high molecular weight component includes an ultra-high molecular weight component having a molecular weight 10 times or more than the maximum peak molecular weight of the low molecular weight component. The content of the ultra-high molecular weight component is 1 to 10% by mass relative to the total amount of the block copolymer. The block copolymer or hydrogenated thereof according to claim 1.

3. The maximum peak molecular weight of the aforementioned low molecular weight component is between 30,000 and 200,000. The block copolymer or hydrogenated thereof according to claim 1.

4. The content of the vinyl aromatic monomer units is 10 to 50% by mass relative to the total amount of the block copolymer. Having a vinyl bond derived from the aforementioned conjugated diene monomer unit, The amount of vinyl bond is 5 to 90 mol% relative to the total amount of conjugated diene monomer units. The block copolymer or hydrogenated thereof according to claim 1.

5. The content of the vinyl aromatic monomer units is 10 to 50% by mass relative to the total amount of the block copolymer. The amount of vinyl bond derived from the conjugated diene monomer units is 5 to 50 mol% relative to the total amount of the conjugated diene monomer units. The hydrogenation rate is 0 to 60 mol% relative to the total amount of unsaturated double bonds in the block copolymer before hydrogenation. The maximum peak molecular weight of the aforementioned low molecular weight component is between 30,000 and 100,000. The block copolymer or hydrogenated thereof according to claim 1.

6. The block copolymer or its hydrogenated product according to claim 5, A tackifier in an amount of 50 to 400 parts by mass per 100 parts by mass of the block copolymer, The block copolymer comprises 10 to 150 parts by mass of a softening agent per 100 parts by mass of the block copolymer. Adhesive composition.

7. The content of the vinyl aromatic monomer units is 20 to 50% by mass relative to the total amount of the block copolymer. The amount of vinyl bond derived from the conjugated diene monomer units is 5 to 50 mol% relative to the total amount of the conjugated diene monomer units. The weight-average molecular weight of the block copolymer is between 150,000 and 400,000. The maximum peak molecular weight of the aforementioned low molecular weight component is between 50,000 and 150,000. The block copolymer or hydrogenated thereof according to claim 1.

8. The content of the block copolymer or its hydrogenated product according to claim 7 is 0.5 to 30% by mass relative to the total amount of asphalt. Composition for modifying asphalt.

9. The content of vinyl aromatic monomers is 10 to 65% by mass relative to the total amount of the block copolymer. The amount of vinyl bond derived from the conjugated diene monomer units is 30 to 90 mol% of the total amount of the conjugated diene monomer units. The hydrogenation rate is 80 to 100 mol% relative to the total amount of unsaturated double bonds in the block copolymer. The maximum peak molecular weight of the aforementioned low molecular weight component is between 50,000 and 200,000. The block copolymer or hydrogenated thereof according to claim 1.

10. The block copolymer described in claim 9 or its hydrogenated form is included, A thermoplastic resin in an amount of 20 to 500 parts by mass per 100 parts by mass of the block copolymer, The block copolymer comprises 10 to 250 parts by mass of a softening agent per 100 parts by mass of the block copolymer. A composition for modifying thermoplastic resins.

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