Resin composition, method for producing modified hydrogenated block copolymer, and molded article

Abstract

A resin composition comprising component (I): a modified block copolymer (I) having a polymer block (A) mainly composed of a vinyl aromatic compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit, and having 0.01% by mass or more of polar groups; and component (II): a resin (II) having polar groups (excluding component (I)), wherein the mass ratio of component (I) to component (II) is (I) / (II) = 1 / 99 to 70 / 30, and component (I) satisfies the following conditions (i) to (iii). <Condition (i)> The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass. <Condition (ii)> The vinyl bond content is 1 to 55%. <Condition (iii)> The hydrogenation rate is 5 to 55%.

Description

Technical Field

[0001] The present invention relates to a resin composition, a method for producing a modified hydrogenated block copolymer, and a molded article. Background Art

[0002] Resin compositions containing high-strength resins such as engineering plastics have excellent rigidity but poor low-temperature properties (impact resistance, toughness). Therefore, various modifiers have been studied.

[0003] For example, Patent Document 1 discloses a polyamide resin composition. In order to improve the impact resistance of the polyamide resin under low temperature conditions, a modified block copolymer is used as an elastomer serving as a modifier. The modified block copolymer comprises a vinyl aromatic compound polymer block A and an olefin compound polymer block B to which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded. The unsaturation degree of the block B is 20% or less, and the amount of the block A is 10 to 23% by mass relative to the total amount of the blocks A and B.

[0004] In addition, Patent Document 2 discloses a resin composition that uses a modified block copolymer as an elastomer serving as a modifier in order to improve the impact resistance of a polyamide resin under low-temperature conditions. The modified block copolymer comprises a vinyl aromatic compound polymer block and a conjugated diene compound polymer block bonded with maleic anhydride, wherein 25% of the conjugated diene compound polymer is hydrogenated, and the amount of the vinyl aromatic compound polymer block is 40% by mass relative to the total amount of the polymer blocks.

[0005] In recent years, as resin products are used in a variety of applications and their usage areas expand, there is a trend toward demand for technologies that impart impact resistance and toughness to engineering plastics and the like at lower temperatures.

[0006] For example, freezers used to store large fish and meat are usually cooled to around -60°C. Therefore, the materials of components such as containers used for storage in the freezer, freezer interior materials, cooling device housings, and refrigerant tanks are required to have sufficient breaking strength and impact resistance for practical use under such low temperature conditions.

[0007] For components such as containers and interior materials that are exposed to ultra-low temperatures, the strength requirements can be easily met by making them out of metal. However, since some of these components are used in mobile devices, there is also a demand for lightweighting by converting their materials into resins.

[0008] To withstand use in ultra-low temperature conditions, high impact resistance is required to prevent any adverse effects on the contents from being impacted during transportation, etc. Furthermore, in situations where rapid cooling is required to cope with a sudden temperature rise, such as when the freezer door is opened, the refrigerant contracts and expands within the cooling device, requiring high toughness for the refrigerant container and piping.

[0009] Furthermore, in the development, storage, and transportation of vaccines, which have recently attracted much attention, processes are required to maintain and store vaccine materials and vaccines at low temperatures of approximately -50°C to -70°C. Consequently, there is a growing demand for molded products with excellent properties under low-temperature conditions.

[0010] Furthermore, cylindrical containers containing liquids such as vaccines can sometimes expand and contract asymmetrically due to temperature fluctuations, requiring high impact resistance and toughness. Furthermore, during transportation, ultra-low temperature freezers are mounted on vehicles, etc., and there is a demand for components, containers, and housings exposed to low temperatures ranging from -50°C to -70°C to be made of resin, thereby achieving weight reduction.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Application Laid-Open No. 3-128964

[0014] Patent Document 2: Japanese Patent Application Laid-Open No. 4-68343 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] However, the resin compositions disclosed in Patent Documents 1 and 2 have a problem in that physical properties such as impact resistance and toughness are insufficient for practical use under ultra-low temperature conditions of -50°C or lower.

[0017] In order to achieve improved physical properties under ultra-low temperature conditions, it is preferred that the tan δ peak temperature of the elastomer used as a modifier be on the lower side of the operating temperature so that the rigidity is low even under ultra-low temperature conditions. However, according to the research of the present inventors, the tan δ peak temperature of the elastomer contained in the resin composition disclosed in Patent Document 1 is on the higher side of the operating temperature of an ultra-low temperature freezer. Therefore, even if the composition can be used at the level of a normal freezer, it has the problem of not being able to obtain physical properties that are practically sufficient under ultra-low temperature conditions.

[0018] Furthermore, the elastomer as a modifier contained in the resin composition disclosed in Patent Document 2 has a tan δ peak temperature on the lower side of the operating temperature, but has a problem of insufficient physical properties such as toughness under ultralow temperature conditions due to its high rigidity.

[0019] Therefore, an object of the present invention is to provide a resin composition having excellent impact resistance and toughness even under ultra-low temperature conditions.

[0020] Means for solving problems

[0021] The present inventors conducted intensive research to solve the above-mentioned problems in the prior art and found that a resin composition containing a modified block copolymer having a specific structure exhibits excellent impact resistance and toughness under ultra-low temperature conditions, thereby completing the present invention.

[0022] That is, the present invention is as follows. [1]

[0024] A resin composition comprising the following components:

[0025] Component (I): a modified block copolymer (I) having a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, and having 0.01% by mass or more of polar groups; and

[0026] Component (II): Resin (II) having a polar group (excluding the above-mentioned component (I)),

[0027] in,

[0028] The mass ratio of the above-mentioned component (I) to the above-mentioned component (II) is (I) / (II)=1 / 99 to 70 / 30,

[0029] The above-mentioned component (I) satisfies the following conditions (i) to (iii).

[0030] <Condition (i)>

[0031] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass.

[0032] <Condition (ii)>

[0033] The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds. When the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0034] <Condition (iii)>

[0035] The polymer block (B) comprises an alkenyl monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5 to 55%. [2]

[0037] The resin composition according to the above-mentioned [1], wherein the component (I) further satisfies the following condition (iv).

[0038] <Condition (iv)>

[0039] When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more. [3]

[0041] The resin composition described in [1] or [2] above, wherein the component (I) is a modified block copolymer having 0.01 to 5% by mass of polar groups. [4]

[0043] The resin composition as described in any one of [1] to [3] above, wherein the component (II) is at least one selected from the group consisting of polyamide resins, acrylic resins, polyacetal resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, epoxy resins and phenol resins. [5]

[0045] The resin composition according to any one of the above-mentioned [1] to [4], comprising at least one stabilizer as component (III). [6]

[0047] The resin composition according to any one of the above-mentioned [1] to [5], wherein the component (I) further satisfies the following condition (v).

[0048] <Condition(v)>

[0049] When a sheet having a thickness of 2 mm obtained by compression-molding the component (I) was measured using a colorimeter, the b value was 30 or less. [7]

[0051] The resin composition according to any one of the above-mentioned [1] to [6], wherein the polar group of the component (I) is contained in the polymer block (B). [8]

[0053] The resin composition according to any one of the above-mentioned [1] to [7], wherein the polar group of the component (I) is at least one selected from the group consisting of an acid anhydride group, a carboxylic acid group, and a hydroxyl group. [9]

[0055] The resin composition according to any one of the above-mentioned [1] to [8], wherein the component (I) further satisfies the following condition (vi).

[0056] <Condition (vi)>

[0057] 5 g of the above-mentioned component (I) was dissolved in 200 mL of toluene and suction filtered using filter paper (thickness 0.2 mm, maximum diameter 6 μm, capture efficiency 65%). The component on the filter paper, calculated from the mass difference between the filter paper after sufficient drying and the filter paper before filtration, was less than 0.3 g.

[10]

[0059] The resin composition as described in any one of the above [1] to [9], further comprising 100 parts by mass or less of a block copolymer (V) as component (V) relative to 100 parts by mass of component (I) in the above resin composition, wherein the block copolymer (V) is a block copolymer having a polymer block (A') mainly composed of a vinyl aromatic compound unit and a polymer block (B') mainly composed of a conjugated diene compound unit and not bonded to a polar group, and satisfies the following conditions (vii) to (ix).

[0060] <Condition (vii)>

[0061] The content of the vinyl aromatic compound unit in the block copolymer (V) is 1 to 30% by mass.

[0062] <Condition (viii)>

[0063] The polymer block (B') of the block copolymer (V) comprises units (a') derived from 1,2-bonds and / or 3,4-bonds and units (b') derived from 1,4-bonds. When the total content of the polymer block (B') is 100%, the content of the units (a') derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0064] <Condition (ix)>

[0065] The polymer block (B') comprises an alkenyl monomer unit (a'1) obtained by hydrogenating the unit (a') derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b'1) obtained by hydrogenating the unit (b') derived from a 1,4-bond. When the total content of the polymer block (B') is 100%, the total content of the alkenyl monomer unit (a'1) and the alkenyl monomer unit (b'1) is 5 to 55%.

[11]

[0067] A method for producing a modified hydrogenated block copolymer comprises the following steps:

[0068] A process for producing a block copolymer comprising a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, satisfying the following conditions (i) and (ii);

[0069] a step of obtaining a hydrogenated block copolymer, wherein the block copolymer is hydrogenated so as to satisfy the following conditions (iii) and (iv) to obtain a hydrogenated block copolymer; and

[0070] In the modification step, the hydrogenated block copolymer is subjected to a modification reaction under melt kneading so that the content of the polar group is 0.01 to 5% by mass.

[0071] <Condition (i)>

[0072] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass.

[0073] <Condition (ii)>

[0074] The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds. When the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0075] <Condition (iii)>

[0076] The polymer block (B) comprises an alkenyl monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5 to 55%.

[0077] <Condition (iv)>

[0078] When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

[12]

[0080] The method for producing a modified hydrogenated block copolymer as described in the above

[11] , wherein the modification step is performed after adding a stabilizer to the hydrogenated block copolymer.

[13]

[0082] The method for producing a modified hydrogenated block copolymer as described in

[11] or

[12] above, wherein the temperature of the hydrogenated block copolymer is set to 150 to 260°C in the modification step.

[14]

[0084] A method for producing a resin composition, which is the method for producing a resin composition according to any one of [1] to

[10] above, wherein the component (I) is obtained by the method for producing a modified hydrogenated block copolymer according to

[11] above.

[15]

[0086] A molded article of the resin composition according to any one of the above [1] to

[10] .

[16]

[0088] The molded article as described in the above-mentioned

[15] , which is a container.

[17]

[0090] The molded article as described in the above-mentioned

[15] is a cylindrical container.

[18]

[0092] The molded body as described in the above-mentioned

[15] is a shell.

[19]

[0094] The molded article as described in the above-mentioned

[15] is a sheet.

[20]

[0096] The molded article as described in the above-mentioned

[15] is a pipe. [twenty one]

[0098] A molded article, comprising a resin composition comprising the following components:

[0099] At least one resin selected from the group consisting of polyamide resins, acrylic resins, polyacetal resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, epoxy resins, and phenol resins; and

[0100] A modified block copolymer having a polymer block (A) mainly composed of a vinyl aromatic compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit,

[0101] in,

[0102] The modified block copolymer is a modified block copolymer having a vinyl aromatic compound unit content of 1 to 30% by mass, a vinyl bond content of 1 to 55% in the polymer block (B) mainly composed of a conjugated diene compound unit, and at least one group selected from the group consisting of anhydride groups, carboxylic acid groups, and hydroxyl groups.

[0103] The molded article satisfies the following conditions (I-1) to (II-1).

[0104] <Condition (I-1)>

[0105] The elongated test piece having a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the molded article had a tensile elongation at break of 15% or more at a tensile speed of 5 mm / min at -50°C.

[0106] <Condition (II-1)>

[0107] A strip test piece having a width of 10 mm, a length of 40 mm, and a thickness of 2 mm obtained from the molded article showed a peak at -60°C or lower in the viscoelasticity measurement under the conditions of a strain of 0.1% and a frequency of 1 Hz. [twenty two]

[0109] The molded article as described in the above

[21] , wherein the hydrogenation rate of the conjugated diene compound unit in the modified block copolymer is 5 to 55%. [twenty three]

[0111] The molded article as described in

[21] above, wherein a notched strip test piece having a width of 10 mm, a length of 80 mm, a thickness of 2 mm, and a notch shape obtained from the molded article as described in

[21] is subjected to a Charpy impact test at -50°C with the impact direction being lateral in accordance with JIS K 7111-1, and the Charpy impact value is 10 kJ / m 2 above. [twenty four]

[0113] The molded article as described in the above-mentioned

[21] , which is a container.

[25]

[0115] The molded article as described in the above-mentioned

[21] is a cylindrical container.

[26]

[0117] The molded body as described in the above-mentioned

[21] , which is a shell.

[0118] Effects of the Invention

[0119] According to the present invention, a resin composition having excellent impact resistance and toughness under ultra-low temperature conditions can be obtained. DETAILED DESCRIPTION

[0120] A specific embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail below.

[0121] It should be noted that the following embodiments are examples for explaining the present invention and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist of the invention.

[0122] [Resin composition]

[0123] The resin composition of this embodiment includes the following components:

[0124] Component (I): a modified block copolymer (I) having a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, and having 0.01% by mass or more of polar groups; and

[0125] Component (II): Resin (II) having a polar group (excluding the above-mentioned component (I)),

[0126] in,

[0127] The mass ratio of the above-mentioned component (I) to the above-mentioned component (II) is (I) / (II)=1 / 99 to 70 / 30,

[0128] The above-mentioned component (I) satisfies the following conditions (i) to (iii).

[0129] <Condition (i)>

[0130] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass.

[0131] <Condition (ii)>

[0132] The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds. When the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0133] <Condition (iii)>

[0134] The polymer block (B) comprises an alkenyl monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5 to 55%.

[0135] By having the above-mentioned configuration, a resin composition having excellent impact resistance and toughness even under ultralow temperature conditions can be obtained.

[0136] It should be noted that, in this specification, "ultra-low temperature conditions" refer to -50°C or lower.

[0137] Furthermore, in the resin composition of the present embodiment, the modified block copolymer (I) (component (I)) preferably satisfies the following condition (iv).

[0138] <Condition (iv)>

[0139] When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

[0140] The constituent component (I) of the resin composition of the present embodiment satisfies the above-mentioned condition (iv), so that the thermal stability of the component (I) is excellent. Thus, during modification and during mixing with the component (II), the high rigidity of the component (I) and the high temperature of the tan δ peak temperature due to the side reactions described later can be suppressed, and a resin composition exhibiting high impact resistance and toughness even under ultra-low temperature conditions can be obtained.

[0141] (ingredient (I))

[0142] The resin composition of the present embodiment contains a modified block copolymer (I) (hereinafter sometimes also referred to as component (I)), which has a polymer block (A) mainly composed of a vinyl aromatic compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit and has 0.01% by mass or more of a polar group.

[0143] The conjugated diene compound is a diene having a pair of conjugated double bonds.

[0144] As conjugated diene compounds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. can be cited but are not limited thereto. Among these, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred. 1,3-butadiene and isoprene are widely available and advantageous in terms of cost, and are also easily copolymerized with styrene, which is widely used as a vinyl aromatic compound. In addition, 1,3-butadiene is the easiest to adjust the tan δ peak temperature, which will be described later, to below ultralow temperature conditions.

[0145] These compounds may be used alone or in combination of two or more.

[0146] The conjugated diene compound unit in this specification refers to a structural unit derived from the conjugated diene compound in a polymer produced by polymerization of the conjugated diene compound.

[0147] Examples of the vinyl aromatic compound include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene.

[0148] These compounds may be used alone or in combination of two or more.

[0149] The vinyl aromatic compound unit in this specification refers to a structural unit derived from the vinyl aromatic compound in a polymer obtained by polymerizing the vinyl aromatic compound.

[0150] In the resin composition of the present embodiment, the component (I) has 0.01% by mass or more of polar groups.

[0151] By having 0.01% by mass or more of polar groups in component (I), affinity or reactivity with component (II) described below is enhanced, and a resin composition exhibiting excellent impact resistance and toughness even under ultralow temperature conditions can be obtained.

[0152] The "polar group" constituting component (I) is an atomic group in which charge is biased between covalently bonded atoms.

[0153] In covalent bonds between heterogeneous atoms such as carbon-oxygen, carbon-nitrogen, carbon-halogen, oxygen-hydrogen, nitrogen-hydrogen, and silicon-hydrogen, charge bias occurs due to the difference in electronegativity between the atoms. Therefore, atomic groups containing heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, and halogens generally exhibit polarity.

[0154] The amount of the polar group added in component (I) relative to 100% by mass of component (I) is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 8.0% by mass, further preferably 0.05% by mass to 6.0% by mass, further more preferably 0.05% by mass to 5.0% by mass, and still further preferably 0.05% by mass to 4% by mass.

[0155] By adjusting the amount of the added "polar group" on component (I) to be from 0.01 mass % to 10 mass %, preferably from 0.01 mass % to 5 mass %, the dispersibility with component (II) described later is improved, and a resin composition exhibiting excellent impact resistance and toughness under ultra-low temperature conditions can be obtained.

[0156] According to the present inventors' findings, although the performance of component (I) will not be directly reduced when the addition amount of polar groups exceeds 10% by mass relative to 100% by mass of component (I), when attempts are made to produce modified block copolymers containing more than 10% by mass, there is a tendency for side reactions such as crosslinking to occur during modification.

[0157] In addition, under the modification conditions in which the addition amount of the polar group relative to 100% by mass of component (I) is greater than 10% by mass, gelation is easily produced. When mixed with the component (II) described later to form a resin composition, it is suppressed by by-products and tends to be difficult to exhibit impact resistance and toughness under ultra-low temperature conditions.

[0158] As a method for reducing the amount of by-products, there can be mentioned a method of suppressing the resin temperature within the preferred temperature range described below and filtering after adding the polar group using a mesh etc. In the melt kneading method described below, when component (I) has a polar group, it is preferable to insert a mesh into the die portion of the extruder; when it is dissolved or dispersed and mixed in a solvent etc. to carry out the reaction, it is preferable to pass the solution after the reaction through a mesh and filter; and a method of using an extruder after removing the solvent and filtering using a mesh in the same manner as in the melt kneading method is preferable.

[0159] Another method for reducing by-products is to add stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers during the production of component (I) within a range that does not hinder the reaction between the polymer and the polar group.

[0160] In addition, under the modification conditions where the addition amount of the polar group is greater than 5% by mass, it is preferred to suppress the resin temperature to the preferred temperature range described below from the perspective of reducing by-products caused by gelation. In addition, since the replacement frequency of the inserted screen tends to increase sharply, resulting in a serious decrease in productivity, it is practically preferred to control the addition amount of the polar group to a level appropriate for the replacement frequency.

[0161] As a method for imparting polar groups to component (I), known methods can be applied without particular limitation. Examples include melt kneading methods; methods in which the components are dissolved or dispersed in a solvent or the like and then reacted; and the like. Other methods include methods such as anionic living polymerization using a polymerization initiator having a functional group and an unsaturated monomer having a functional group; methods in which a functional group is formed at an active terminal; and methods in which a modifier containing a functional group is subjected to an addition reaction. However, melt kneading methods are preferred.

[0162] In order to adjust the amount of polar groups added to component (I) to preferably 10% by mass or less, more preferably 5% by mass or less, the resin temperature during melt kneading in the melt kneading method is preferably 130°C or higher, more preferably 150°C or higher, and even more preferably 160°C or higher. The preferred upper limit of the resin temperature during melt kneading is 280°C or lower, more preferably 260°C or lower, and even more preferably 250°C or lower.

[0163] Regarding the amount of the modifier added when adding a polar group to component (I), from the perspective of controlling the preferred resin temperature as described above and making the amount of polar group added preferably 10% by mass or less, more preferably 5% by mass or less, the amount added is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5.5 parts by mass or less, and even more preferably 3.5 parts by mass or less, based on 100 parts by mass of the block copolymer.

[0164] When adding a polar group to component (I), when the modification reaction is carried out by dissolving or dispersing and mixing in a solvent or the like, or when a method is used to carry out an addition reaction at an active terminal by anionic living polymerization, the reaction temperature is preferably 250°C or lower, more preferably 200°C or lower. Furthermore, by calculating the reaction rate of the modifier and component (I) at any reaction temperature, the amount of polar group added can be controlled to 10% by mass or lower, preferably 5% by mass or lower, by adjusting the amount of the reactive sites of component (I) and the modifier to an appropriate ratio.

[0165] Examples of the above-mentioned “polar group” include, but are not limited to, an atomic group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acyl halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thialdehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilyl group, a tin halide group, a boric acid group, a boron-containing group, a borate group, an alkoxytin group, and a phenyltin group.

[0166] Particularly preferably, there is at least one atomic group of the functional group selected from the group consisting of anhydride groups, carboxylic acid groups, hydroxyl groups, epoxy group(s), amino group(s), amide groups, silanol groups and alkoxysilyl groups, more preferably there is at least one atomic group of the functional group selected from the group consisting of anhydride groups, carboxylic acid groups, hydroxyl groups, epoxy group(s), amino group(s), amide groups, more preferably there is at least one atomic group of the functional group selected from the group consisting of anhydride groups, carboxylic acid groups, hydroxyl groups. In the formation process of the polar group, when anhydride is bonded to the block copolymer, moisture in the air etc. reacts with anhydride, and a part may become carboxylic acid groups and form a polar group, but its amount is not particularly limited. That is, in this specification, "at least one functional group selected from the group consisting of anhydride groups, carboxylic acid groups, hydroxyl groups" includes following manner: in the modification process, after anhydride groups are added as polar groups, hydration of anhydride is actively or unintentionally carried out and changed into carboxylic acid groups or hydroxyl groups.

[0167] The above-mentioned "polar group" can be formed using a modifier.

[0168] Examples of the modifier include, but are not limited to, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N-methylpyrrolidone, maleic acid, maleic anhydride, maleic anhydride imide, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, glycidyl methacrylate, and crotonic acid.

[0169] Other methods for forming a "polar group" in component (I) include reacting an organic alkali metal compound such as an organic lithium compound with a block copolymer (metallation reaction), and then adding a modifier having a functional group to the block polymer to which the organic alkali metal has been added.

[0170] In component (I), the portion having a "polar group" is preferably the polymer block (B) constituting component (I).

[0171] Bonding to polymer block (B) refers to a state in which a polar group is bonded to a double bond contained in polymer block (B) through an addition reaction. Polymer block (B) still contains double bonds derived from a conjugated diene after the hydrogenation reaction. By kneading a compound having a polar group with the block copolymer in a melt kneading step, a modified block copolymer containing a polar group in polymer block (B) can be obtained.

[0172] When the polymer block (B) is present at the end of the block copolymer, the polymer block (B) can be provided with a polar group by reacting a polymerization initiator having a functional group or reacting a modifier containing a functional group with the active end of the block copolymer. However, in the present embodiment, such a polar group is not bonded to the terminal conjugated diene compound unit.

[0173] Adding a "polar group" to the polymer block (B) of the block copolymer tends to improve compatibility between component (II) and component (I) described below, and tends to improve impact resistance and toughness under ultralow temperature conditions.

[0174] Methods for confirming the bonding position of the "polar group" include analysis using a nuclear magnetic resonance apparatus, and measurement using matrix-assisted laser desorption / ionization, etc., by decomposing the residual double bonds of the polymer block (B) by an appropriate method.

[0175] Component (I) is a hydrogenated product of a modified block copolymer having a polymer block (A) mainly composed of a vinyl aromatic compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit.

[0176] The polymer block (A) constituting the component (I) mainly comprises vinyl aromatic compound units.

[0177] Here, "mainly" means that the vinyl aromatic compound unit accounts for 70% by mass or more based on the total mass of the polymer block (A).

[0178] The content of the vinyl aromatic compound unit in the polymer block (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass (without intentional addition of other monomers), based on the total mass of the polymer block (A).

[0179] The polymer block (B) constituting the component (I) mainly comprises a conjugated diene compound unit.

[0180] Here, "mainly" means that the conjugated diene compound unit accounts for 70% by mass or more based on the total mass of the polymer block (B).

[0181] The content of the conjugated diene compound unit in the polymer block (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass, based on the total mass of the polymer block (B).

[0182] The content of the polymer block (A) in the component (I) can be determined by the following formula, for example, using a method (described in IMKOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) in which a block copolymer before hydrogenation is subjected to oxidative decomposition using tert-butyl hydroperoxide using osmium tetroxide as a catalyst, using the mass of the block component of the vinyl aromatic compound (excluding the block component of the vinyl aromatic compound having an average degree of polymerization of about 30 or less).

[0183] Polymer block (A) content (mass %) = (mass of the vinyl aromatic compound block component in the block copolymer before hydrogenation / mass of the block copolymer before hydrogenation) × 100

[0184] Component (I) may be a block copolymer having a polymer block (A) and a polymer block (B) as basic skeletons, wherein these basic skeletons have a repeating structure.

[0185] Furthermore, component (I) may be a block copolymer obtained by coupling the basic skeletons of polymer block (A) and polymer block (B).

[0186] The modified block copolymer (I) contained in the resin composition of the present embodiment satisfies the following conditions (i) to (iii).

[0187] <Condition (i)>

[0188] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass.

[0189] By setting the content of the vinyl aromatic compound unit in the modified block copolymer (I) to 30% by mass or less, the modified block copolymer (I) is in a rubbery state under ultralow temperature conditions, has low rigidity, and is excellent in impact resistance and toughness.

[0190] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is preferably 3 to 28% by mass, more preferably 5 to 27% by mass, and even more preferably 7 to 25% by mass.

[0191] Furthermore, by setting the content of the vinyl aromatic compound unit in the modified block copolymer (I) to 1% by mass or more, excellent processability can be obtained.

[0192] The content of the vinyl aromatic compound unit in the modified block copolymer (I) can be controlled within the above numerical range by adjusting polymerization conditions such as the amount of monomer added, the timing of addition, and the polymerization temperature.

[0193] <Condition (ii)>

[0194] The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds. When the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0195] <Condition (iii)>

[0196] The polymer block (B) comprises alkenyl monomer units (a1) obtained by hydrogenating the units (a) derived from 1,2-bonds and / or 3,4-bonds (alkenyl monomer units hydrogenated as the units derived from 1,2-bonds and / or 3,4-bonds) and alkenyl monomer units (b1) obtained by hydrogenating the units (b) derived from 1,4-bonds (alkenyl monomer units hydrogenated as the units (b) derived from 1,4-bonds). When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer units (a1) and the alkenyl monomer units (b1) is 5 to 55%.

[0197] The reason why impact resistance and toughness are generally imparted to highly rigid resins such as engineering plastics by dispersing specific elastomers is that when an impact or stretch is applied, pores are generated at the interface between the resin and the dispersed elastomer particle components or in the elastomer particles themselves, and the matrix resin undergoes shear yield starting from the elastomer particles, thereby causing stress relaxation.

[0198] At this time, if the rigidity of the elastomer particles relative to the matrix resin is low, stress concentration occurs at the interface. Therefore, in order to achieve a high modification effect even under ultra-low temperature conditions, the elastomer component must have low rigidity under ultra-low temperature conditions. Therefore, in order to achieve high impact resistance and toughness under ultra-low temperature conditions, it is important that the elastomer component be in a low-rigidity rubbery state at these temperatures.

[0199] Whether an elastomer is in a rubbery state under certain temperature conditions can be approximately determined by the temperature at which its main chain produces micro-Brownian motion (primary dispersion), that is, the primary dispersion peak temperature of the tanδ curve in the viscoelastic spectrum. At a temperature higher than the primary dispersion peak temperature, the elastomer appears to be in a rubbery state.

[0200] The tan δ curve in the viscoelastic spectrum can be measured by the method described in the Examples below. In the resin composition of this embodiment, the at least one tan δ peak temperature caused by the polymer block (B) is preferably below -55°C, more preferably below -60°C, and even more preferably below -65°C.

[0201] The tan δ peak temperature is mainly determined by the bonding state and hydrogenation amount of the polymer block (B) mainly composed of conjugated diene compound units.

[0202] The modified block copolymer (I) constituting the resin composition of this embodiment preferably has a main dispersion peak of the tan δ curve in the viscoelastic spectrum at -55°C or lower, more preferably -60°C or lower, and even more preferably -65°C or lower.

[0203] The "main dispersion peak of the tan δ curve" refers to the maximum value of the tan δ curve before melting due to the movement of the main chain in the molecular structure. By setting the temperature at this maximum value to -55°C or below, excellent impact resistance and toughness under ultra-low temperature conditions are achieved.

[0204] The "main dispersion peak of the tan δ curve" can be measured by the method described in the examples below.

[0205] The polymer block (B) comprises units (a) derived from 1,2-linkages and / or 3,4-linkages and units (b) derived from 1,4-linkages. The content of the units (a) is 55% or less, taking the total content of the polymer block (B) as 100%. This allows the main dispersion peak temperature of the tan δ curve of the modified block copolymer (I) to be -55°C or less. Furthermore, from the perspective of processability, the content of the units (a) is 1% or more.

[0206] When the total content of the polymer block (B) is 100%, the content of the unit (a) is preferably 5 to 50%, more preferably 10 to 45%, and even more preferably 15 to 40%.

[0207] The content of the units (a) can be controlled by using a regulator such as a polar compound during the polymerization of the component (I).

[0208] As the adjusting agent, for example, a tertiary amine compound or an ether compound may be added, and a tertiary amine compound is preferably used.

[0209] The tertiary amine compound is a general formula R 1 R 2 R 3 N(where R 1 、R 2 、R 3 is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group).

[0210] Examples of tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperazine, N,N,N',N",N"-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine.

[0211] The polymer block (B) of the modified block copolymer (I) comprises an alkenyl monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-linkage and / or a 3,4-linkage, and an alkenyl monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-linkage. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5 to 55%.

[0212] By setting the total content of the alkenyl monomer units (a1) and the alkenyl monomer units (b1) to 55% or less, the main dispersion peak temperature of the tan δ curve of the modified block copolymer (I) can be set to -55°C or less.

[0213] Furthermore, by making the total content 1% or more, excellent thermal stability can be obtained.

[0214] The total content of the alkenyl monomer units (a1) and the alkenyl monomer units (b1) in the polymer block (B) is preferably 5 to 50%, more preferably 10 to 45%, and even more preferably 15 to 40%.

[0215] The total content of the ethylenic monomer units (a1) and (b1) in the polymer block (B) can be controlled within the above numerical range by appropriately adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, etc. in the hydrogenation method described below.

[0216] The method for hydrogenating the modified block copolymer (I) is not particularly limited, and conventionally known methods can be applied.

[0217] As hydrogenation catalysts, for example, the following can be used: (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silicon oxide, aluminum oxide, diatomaceous earth, and the like; (2) so-called Ziegler-type hydrogenation catalysts in which organic acid salts or transition metal salts such as acetylacetonate of Ni, Co, Fe, and Cr and reducing agents such as organic aluminum; and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, and Zr.

[0218] Specific examples of the hydrogenation catalyst include those described in JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, and JP-B-2-9041.

[0219] Preferred hydrogenation catalysts include cyclopentadienyl titanium compounds and / or reducing organometallic compounds.

[0220] As the titanium cyclopentadienyl compound, the compounds described in Japanese Patent Application Laid-Open No. 8-109219 can be used. Examples of titanium cyclopentadienyl compounds include compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and mono(pentamethylcyclopentadienyl)titanium trichloride. The titanium cyclopentadienyl compound may contain one or a combination of two of the above skeletons.

[0221] Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

[0222] The hydrogenation catalyst may be used alone or in combination of two or more.

[0223] Furthermore, as described above, it is important that the modified block copolymer (I) is in a rubbery state and has low rigidity under ultralow temperature conditions.

[0224] By setting the content of the vinyl aromatic compound unit in the modified block copolymer (I) to 30% by mass or less, the modified block copolymer (I) becomes a rubbery state with low rigidity at ultralow temperatures, thereby achieving excellent impact resistance and toughness.

[0225] Furthermore, the modified block copolymer (I) contained in the resin composition of the present embodiment preferably satisfies the following condition (iv).

[0226] <Condition (iv)>

[0227] When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) mainly composed of conjugated diene compound units is taken as 100%, the total content of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

[0228] Since the "resin (II) having a polar group" constituting the resin composition of the present embodiment has a polar group, it is preferable that the melting temperature be high from the viewpoint of entropy and enthalpy.

[0229] Furthermore, component (I) has a polar group as described above. When the polar group is bonded to the block copolymer by melt kneading, it melts at high temperatures and is subject to shear. Therefore, when exposed to high temperatures, side reactions such as crosslinking occur, resulting in increased rigidity and a higher tan δ peak temperature, potentially leading to a decrease in impact resistance and toughness under ultra-low temperature conditions.

[0230] That is, the tan δ peak temperature tends to shift to a higher temperature side due to side reactions such as crosslinking during modification. Therefore, in component (I), it is preferable to suppress the increase in the tan δ peak temperature by increasing the vinyl hydrogenation rate.

[0231] From the perspective of suppressing an increase in the tan δ peak temperature, the tan δ peak temperature of the "modified block copolymer" constituting component (I) is preferably increased by 10°C or less, more preferably 7°C or less, even more preferably 5°C or less, and even more preferably 3°C or less, compared to the tan δ peak temperature of the "unmodified block copolymer" before the polar groups are bonded.

[0232] Furthermore, since the "units (a) derived from 1,2-bonding and / or 3,4-bonding" constituting component (I) have double bonds in the side chains, the above-mentioned side reactions are considered to occur more easily than the "units (b) derived from 1,4-bonding".

[0233] Therefore, from the perspective of suppressing the increase in rigidity and the increase in the tan δ peak temperature due to the above-mentioned side reactions and fully expressing the impact resistance and toughness under ultra-low temperature conditions, the hydrogenation rate of the "units (a) derived from 1,2-bonds and / or 3,4-bonds", that is, the proportion of the alkenyl units (a1) when the units (a) are 100%, is preferably 80% or more, more preferably 83% or more, and even more preferably 85% or more.

[0234] It should be noted that when the total content of the alkenyl units (a1) and the alkenyl units (b1) is less than the content of the units (b) derived from the 1,4-bond, the amount of the alkenyl units (b1) is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more relative to the total amount of the alkenyl units (a1) and (b1).

[0235] This can suppress the increase in rigidity and the increase in tan δ peak temperature due to the above-mentioned side reactions, and can exhibit excellent impact resistance and toughness in an ultra-low temperature environment.

[0236] From the perspective of ensuring that the hydrogenation rate of the above-mentioned units (a), that is, the ratio of the alkenyl units (a1) when the units (a) are 100%, is 80% or more, the temperature during the hydrogenation reaction is preferably 55 to 200°C, more preferably 60 to 170°C, further preferably 65 to 160°C, and even more preferably 70 to 150°C.

[0237] The pressure of hydrogen 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.

[0238] The hydrogenation reaction time is usually 3 minutes to 10 hours, and preferably 10 minutes to 5 hours.

[0239] The hydrogenation reaction can be carried out in a batch process, a continuous process, or a combination thereof.

[0240] In the resin composition of the present embodiment, the component (I) preferably satisfies the following <condition (v)>.

[0241] <Condition(v)>

[0242] When a sheet having a thickness of 2 mm obtained by compression-molding the component (I) was measured using a colorimeter, the b value was 30 or less.

[0243] The above condition (v) is set with attention paid to the fact that the color tone of component (I) affects the performance of the resin composition of this embodiment. Therefore, the b value measured by molding a sheet composed only of component (I) is used as an index.

[0244] According to the use of the resin composition of the present embodiment, in order to color the resin composition, the following situation is considered: as the pre-stage of the process of mixing component (I) with component (II), pigments and / or colorants such as carbon black, titanium oxide, etc. as component (III) described later are added to component (I) to color component (I). Even in such a case, since condition (v) is the b-value of the sheet of component (I) in a state not including a coloring component, the thickness 2mm sheet used for b value determination needs to be molded before adding the coloring component or component (III) is removed before making. The b-value of the above-mentioned component (I) is measured without adding a pigment and / or coloring agent.

[0245] As the method for removing coloring component from the resin composition comprising coloring component, it is not limited, for example, reprecipitation can be enumerated. In the case where pigment or coloring agent are organic or inorganic etc. and are dissolved in the poor solvent of the component (I) of methanol, ethanol etc., component (I) and the mixture of component (III) described later are dissolved in the good solvents such as toluene, cyclohexane, dimethylbenzene with a concentration of less than 20 mass %, carefully added dropwise to the poor solvent being more than 50 times of amount relative to the good solvent, thus can be separated. In addition, in the case where pigment or coloring agent are particulates such as carbon black and / or in the poor solvent of above-mentioned component (I), it may be difficult to remove using above-mentioned reprecipitation, therefore it is possible to share and / or use removal process, the removal process is carried out by centrifugation, the filtration performed by various filters using the particle diameter suitable for additive, the separation using the high appropriate post of the interaction of additive.

[0246] When the b value of a 2 mm thick sheet of component (I) is 30 or less, the resin composition of this embodiment, formed by mixing the component (I) with component (II), exhibits excellent appearance and color development, and tends to prevent the coloring component described later from reducing toughness and impact resistance under ultra-low temperature conditions. From this perspective, the b value of a 2 mm thick sheet of component (I) is preferably controlled to be 30 or less, more preferably 25 or less, even more preferably 23 or less, and even more preferably 20 or less.

[0247] In the production of component (I), it is generally known that the coloring component of component (I) and its generation mechanism utilizes, but is not limited to, chromogenic group structures having unsaturated bonds such as -C=O, -N=N-, and -N=O, and auxochrome structures such as -OR, -OH, -NH2, -NHR, -SO3H, and -COOH to cause color change. These structures, similar structures, structures presumed to be generated by reaction with atmospheric oxygen and nitrogen, and structures presumed to be generated by thermal decomposition, etc., are often included in conventional antioxidants and the modifiers described below.

[0248] Furthermore, when an antioxidant reacts with oxygen, nitrogen, or the like in the atmosphere to form a chromogenic group structure or an auxochrome group structure, the effect of suppressing side reactions such as crosslinking is reduced, and the increase in the tan δ peak temperature cannot be suppressed, which tends to reduce the sufficient toughness and impact resistance under ultra-low temperature conditions. Furthermore, when a modifier reacts with oxygen, nitrogen, or the like in the atmosphere to form a chromogenic group structure or an auxochrome group structure, the compatibility between component (I) and component (II) is altered, which tends to reduce the sufficient toughness and impact resistance under ultra-low temperature conditions.

[0249] Therefore, from the perspective of reducing the generation of the above-mentioned coloring components and making the b value of a sheet of component (I) with a thickness of 2 mm 30 or less, the amount of the modifier added to component (I) is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5.5% by mass or less, and even more preferably 3.5% by mass or less relative to component (I).

[0250] When the amount of the modifier is 10% by mass or less, the modifier can be prevented from becoming a coloring component when imparting a polar group, and there is a tendency to prevent the b value of the modified block copolymer (I) from increasing.

[0251] In addition, as described below, the resin composition of the present embodiment can contain at least one stabilizer. From the aspect of reducing the generation of the above-mentioned coloring component, making the b value of the sheet of the thickness 2mm of component (I) be less than 30, if component (I) is 100 mass %, the addition amount of the above-mentioned stabilizer is preferably less than 6 mass %, more preferably less than 5 mass %, further preferably less than 4 mass %, further more preferably less than 3 mass %. When the amount of stabilizer is less than 6 mass %, it is possible to suppress the modifier from becoming a coloring component when polar groups are given to component (I), with the tendency that the b value of the modified block copolymer (I) can be prevented from increasing.

[0252] Particularly in the resin combination of the present embodiment, when using a stabilizer and a modifier comprising an aromatic ring, the polymerization initiator of the block copolymer and the residual metal of the catalyst residue in the hydrogenation reaction are coordinated on the aromatic ring. When the electron density decreases, the reactivity of the compound of the stabilizer and the modifier is improved, and they react easily with oxygen in the air, thereby further generating a tendency of a coloring component comprising the chromogenic group and / or auxiliary color group. Thus, in order to make the b value of the sheet of the thickness of 2mm of the above-mentioned component (I) less than 30, the residual metal amount of the polymerization initiator and the catalyst residue is preferably less than 120ppm, more preferably less than 80ppm, further preferably less than 70ppm, and further more preferably less than 50ppm.

[0253] When the residual metal content is 120 ppm or less, when a polar group is imparted to component (I), the stabilizer and / or modifier can be inhibited from becoming a coloring component, and an increase in the b value of the modified block copolymer tends to be prevented.

[0254] Furthermore, in order to reduce the amount of the aforementioned by-products, the resin temperature is suppressed within the preferred temperature range described below during the production process of component (I), and the residual metal amount is controlled to be within the aforementioned preferred range when filtering using a mesh or the like after the addition of the polar group. This tends to reduce the frequency of mesh replacement and improve productivity.

[0255] The residual metal component is not particularly limited, and examples thereof include Ti, Li, Mg, Fe, and compounds containing these metals.

[0256] As a method for removing the residual metal components, conventionally known methods can be applied without particular limitation. For example, a method in which water and carbon dioxide are added after the hydrogenation reaction of the block copolymer to neutralize the hydrogenation catalyst residue; a method in which an acid is added in addition to water and carbon dioxide to neutralize the hydrogenation catalyst residue; etc., but the method is not limited to these. Specifically, the method described in Japanese Patent Application No. 2014-557427 can be cited as a preferred method.

[0257] Furthermore, in the step of obtaining the modified block copolymer (I), the resin temperature of component (I) is preferably 130°C to 280°C or lower from the perspective of reducing the formation of the aforementioned coloring components and controlling the b value of a 2 mm thick sheet to 30 or lower. Since reactions at high temperatures are known to particularly affect the formation of coloring components, the upper limit is more preferably 260°C or lower, and even more preferably 250°C or lower. The lower limit of the resin temperature can be set from the perspective of ensuring the productivity of component (I), and is preferably 150°C or higher, and more preferably 160°C or higher, depending on factors such as the reactivity of the polar group and the amount added.

[0258] The resin temperature refers to the temperature of the component (I) in a molten state during the desolvation process, and can be measured by bringing any thermometer or temperature sensor into contact with the resin.

[0259] In particular, in the aforementioned melt kneading method, when polar groups are imparted to the block copolymer as a modification step, the resin temperature in the extruder, as measured by the method described in the Examples, is preferably 130°C to 280°C. As described above, the preferred upper limit is 260°C or lower, more preferably 250°C or lower. The preferred lower limit is 150°C or higher, more preferably 160°C or higher.

[0260] Conjugated double bonds are known as a common coloring mechanism. Therefore, when using a modifier containing double bonds and adding the polar group by melt kneading as a modification step, the hydrogenated block copolymer is preferably heated at a temperature of 130°C to 280°C, more preferably 150°C to 260°C, and even more preferably 160°C to 250°C, to prevent the residual double bonds in the conjugated diene polymer block of the hydrogenated block copolymer from thermally decomposing and becoming conjugated double bonds, thereby causing coloration.

[0261] In the resin composition of the present embodiment, the component (I) preferably satisfies the following <condition (vi)>.

[0262] <Condition (vi)>

[0263] 5 g of component (I) was dissolved in 200 mL of toluene and suction filtered using filter paper (thickness 0.2 mm, maximum diameter 6 μm, capture efficiency 65%). After sufficient drying, the component on the filter paper, calculated from the mass difference between the filter paper after filtration and the filter paper before filtration, was less than 0.30 g.

[0264] The components on the filter paper are presumably crosslinked components generated by complex reactions between the block copolymers during the desolventizing step after polymerization of the block copolymer and / or the modification step of the block copolymer during melt kneading, as well as by reactions between the block copolymers via a modifier. When included in component (I), these crosslinked components tend to increase rigidity under ultralow temperature conditions, thereby reducing toughness and impact resistance under ultralow temperature conditions.

[0265] In the above filtration, the amount of the component on the filter paper is preferably 0.3 g or less, more preferably 0.25 g or less, even more preferably 0.2 g or less, and even more preferably 0.15 g or less.

[0266] In the step of obtaining the modified block copolymer (I), particularly in the melt kneading method, when polar groups are imparted to the block copolymer, it is believed that the above-mentioned side reactions are promoted in a high temperature state and / or in the presence of a large amount of modifier. Therefore, it is preferable to control the resin temperature and / or the amount of modifier to be within the same range as the above-mentioned condition (v). Even if condition (v) is satisfied, when the amount of the component on the filter paper during the above-mentioned filtration exceeds 0.3 g, there is a tendency that sufficient toughness and impact resistance under ultra-low temperature conditions may not be exhibited, such as when the amount of residual metal is extremely small.

[0267] Even if the crosslinked components are removed by the mesh or the like and the content on the filter paper is 0.3 g or less, if condition (v) is not satisfied, the toughness and impact resistance under ultralow temperature conditions tend to decrease.

[0268] That is, from the viewpoint of suppressing the above-mentioned side reactions and suppressing the crosslinking component, the resin temperature in the step of obtaining the modified block copolymer component (I) is preferably 130° C. to 280° C. or lower.

[0269] Reactions under high temperature conditions are believed to particularly affect the formation of crosslinking components, so the upper limit of the resin temperature is more preferably 260°C or lower, and even more preferably 250°C or lower. The lower limit of the resin temperature can be set from the perspective of ensuring productivity, but is preferably set to 150°C or higher, and more preferably 160°C or higher, depending on the reactivity of the polar group, the amount of addition, and other factors.

[0270] The resin temperature refers to the temperature of the component (I) in a molten state during the desolvation process, and can be measured by bringing any thermometer or temperature sensor into contact with the resin.

[0271] In particular, in the melt kneading method described above, when polar groups are imparted to the block copolymer, the resin temperature in the extruder, as measured by the method described in the Examples below, is preferably 130°C to 280°C. As described above, the preferred upper limit is 260°C or lower, more preferably 250°C or lower. The preferred lower limit is 150°C or higher, more preferably 160°C or higher.

[0272] In addition, from the perspective of suppressing the generation of crosslinking components by the modifier, the amount of the modifier added is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5.5 parts by mass or less, and even more preferably 3.5 parts by mass or less, relative to 100 parts by mass of component (I). By setting the amount of the modifier to 10 parts by mass or less, it is possible to suppress the increase in crosslinking components of the block copolymer by the modifier when imparting polar groups.

[0273] The weight average molecular weight of the modified block copolymer (I) (component (I)) is preferably 5×10 3 ~1×10 6 , more preferably 1×10 4 ~5×10 5 , more preferably 3×10 4 ~3×10 5 , and more preferably 5×10 4 ~2×10 5 .

[0274] By making the weight average molecular weight of the modified block copolymer (I) 5×10 3 The above mentioned properties tend to be excellent in impact resistance under ultra-low temperature conditions. 5 The following tends to have excellent moldability.

[0275] From the perspective of improving moldability and achieving excellent impact resistance and toughness under ultralow temperature conditions, the molecular weight distribution of the modified block copolymer (I) preferably has a lower limit of 1.00 or greater, more preferably 1.0 or greater, and even more preferably 1.04 or greater. The preferred upper limit is 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less.

[0276] (Method for producing component (I))

[0277] The modified block copolymer (I) can be obtained, for example, by conducting anionic living polymerization in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound.

[0278] Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0279] Examples of polymerization initiators include organic alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds, which are generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds. Examples of alkali metals include lithium, sodium, and potassium.

[0280] Examples of the organic alkali metal compound include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, including compounds containing one lithium in one molecule, and dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithiums in one molecule.

[0281] Specific examples of the organic alkali metal compound include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, the reaction product of diisopropenylbenzene and sec-butyllithium, and the reaction product of divinylbenzene with sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, 1-(tert-butoxy)propyllithium disclosed in U.S. Patent No. 5,708,092 and lithium compounds having one to several molecules of isoprene inserted therein to improve solubility, alkyllithiums containing silyl groups such as 1-(tert-butyldimethylsilyloxy)hexyllithium disclosed in British Patent No. 2,241,239, alkyllithiums containing amino groups disclosed in U.S. Patent No. 5,527,753, and lithium amides such as lithium diisopropylamine and lithium hexamethyldisilazide can also be used.

[0282] As a method for polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied.

[0283] Examples of the polymerization method include batch polymerization, continuous polymerization, and a combination thereof. Any of these methods may be used. Batch polymerization is particularly preferred for obtaining a block copolymer having excellent heat resistance.

[0284] The polymerization temperature is preferably 0°C to 180°C, more preferably 30°C to 150°C. The polymerization time varies depending on the conditions, but is generally within 48 hours, preferably 0.1 to 10 hours. In addition, as the atmosphere of the polymerization system, an inert gas atmosphere such as nitrogen is preferred. Regarding the polymerization pressure, there is no particular limitation as long as it is set within a pressure range that can maintain the monomer and solvent in a liquid phase within the above-mentioned temperature range. In addition, care must be taken not to allow impurities such as water, oxygen, and carbon dioxide, which may inactivate the catalyst and the active polymer, to be mixed into the polymerization system.

[0285] Furthermore, after the polymerization step is completed, a coupling reaction may be carried out by adding a desired amount of a bifunctional or higher functional coupling agent.

[0286] As the bifunctional coupling agent, conventionally known coupling agents can be used without particular limitation.

[0287] Examples of the bifunctional coupling agent include alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dihalides such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0288] In addition, as a trifunctional or higher multifunctional coupling agent, a conventionally known coupling agent can be used without particular limitation. Examples of trifunctional or higher multifunctional coupling agents include trivalent or higher polyols; polyvalent epoxy compounds such as epoxidized soybean oil, diglycidyl bisphenol A, and 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane; and compounds of the general formula R4-nSiX n (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4) a silicon halide compound represented by, for example, methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride, and bromides thereof; general formula R4-nSnX n (Here, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4) a tin halide compound represented by, for example, polyvalent halides such as methyltin trichloride, tert-butyltin trichloride, and tin tetrachloride. In addition, dimethyl carbonate, diethyl carbonate, etc. can also be used.

[0289] The modified block copolymer (I) solution obtained as described above can be separated from the solution by removing catalyst residues as needed.

[0290] Examples of methods for separating the solvent include: adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated copolymer, to the hydrogenated reaction solution to precipitate the polymer and recover it; adding the reaction solution to hot water with stirring and removing the solvent by steam stripping to recover it; or directly heating the polymer solution to distill off the solvent. It should be noted that stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers may be added to the hydrogenated copolymer.

[0291] (Method for producing modified hydrogenated block copolymer)

[0292] As described above, the resin composition of the present embodiment contains the component (I): a modified block copolymer and the component (II): a resin having a polar group.

[0293] Component (I) is preferably a modified hydrogenated block copolymer produced by the production method shown below.

[0294] That is, the method for producing the modified hydrogenated block copolymer comprises the following steps:

[0295] A process for producing a block copolymer comprising a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, satisfying the following conditions (i) and (ii);

[0296] A step of obtaining a hydrogenated block copolymer, comprising hydrogenating the block copolymer according to the following conditions (iii) and (iv) to obtain a hydrogenated block copolymer; and

[0297] In the modification step, the hydrogenated block copolymer is subjected to a modification reaction under melt kneading so that the content of the polar group is 0.01 to 5% by mass.

[0298] <Condition (i)>

[0299] The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1 to 30% by mass.

[0300] <Condition (ii)>

[0301] The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds. When the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0302] <Condition (iii)>

[0303] The polymer block (B) comprises an alkenyl monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5 to 55%.

[0304] <Condition (iv)>

[0305] When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

[0306] In the method for producing the modified hydrogenated block copolymer, it is preferred that the block copolymer be hydrogenated to obtain the hydrogenated block copolymer, and then the stabilizer be added, followed by a modification step.

[0307] Examples of the stabilizer include various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers.

[0308] This can reduce by-products.

[0309] In the modification step, the temperature of the hydrogenated block copolymer is preferably set to 150°C to 260°C.

[0310] The more preferred upper limit is 250° C. or lower. The preferred lower limit is 150° C. or higher, and more preferably 160° C. or higher.

[0311] Conjugated double bonds are known as a common coloring mechanism. Therefore, when a modifier containing double bonds is used and the polar group is added by melt kneading as a modification step, the temperature of the hydrogenated block copolymer is preferably 150-260°C, more preferably 160-250°C, to prevent the residual double bonds in the hydrogenated block copolymer from thermally decomposing and converting into conjugated double bonds, which may cause coloring.

[0312] Since the modified block copolymer (component (I)) constituting the resin composition of the present embodiment is excellent in toughness at room temperature and under ultralow temperature conditions, the resin composition of the present embodiment also tends to be excellent in toughness.

[0313] The toughness of component (I) can be determined in accordance with JIS K 6251. The elongation at break at room temperature under a tensile speed of 500 mm / min is preferably 500% or more, more preferably 550% or more, and even more preferably 600% or more. Furthermore, the elongation at break at -60°C under a tensile speed of 5 mm / min is preferably 100% or more, more preferably 150% or more, even more preferably 200% or more, even more preferably 250% or more, and even more preferably 300% or more.

[0314] (Component (II): Resin (II) having a polar group)

[0315] The resin composition of the present embodiment contains a resin (II) having a polar group (hereinafter sometimes referred to as component (II)).

[0316] Component (II) is different from component (I) in that it is a modified block copolymer (I) having a "polar group".

[0317] The polar group in the component (II) improves its dispersibility with the component (I) and allows the component (II) to exhibit excellent impact resistance and toughness under ultra-low temperature conditions.

[0318] Here, examples of the “polar group” possessed by component (II) include, but are not limited to, an atomic group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thialdehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxy group, an alkoxide group, an alkoxysilyl group, a tin halide group, a boronic acid group, a boron-containing group, a borate group, an alkoxytin group, a phenyltin group, a phenol group, and a mercapto group.

[0319] Furthermore, the component (II) preferably has "affinity" or "reactivity" with the polar group bonded to the component (I), and more preferably has "reactivity".

[0320] Here, "reactivity" means that the polar groups of component (I) and component (II) have covalent bonding properties with each other.

[0321] When polar groups react with each other, for example, when the OH group of a carboxyl group is detached or hydrogen is added to an amino group and detached, the original polar group changes or disappears, and when a covalent bond is formed, it is included in the definition of polar groups showing "reactivity" with each other.

[0322] Furthermore, "affinity" means that the polar groups of component (I) and component (II) do not form a covalent bond but are easily aggregated or bonded to each other, and examples thereof include ionic bonding and hydrogen bonding.

[0323] Examples of the combination of "polar groups" include:

[0324] Amino group and carboxylic acid group, carbonyl group, epoxy group, hydroxyl group, acid anhydride group, sulfonic acid group, aldehyde group;

[0325] Isocyanate group and hydroxyl group, carboxylic acid;

[0326] anhydride group and hydroxyl group;

[0327] silanol groups, hydroxyl groups, and carboxylic acid groups;

[0328] Epoxy and carboxylic acid;

[0329] Halogen and carboxylic acid group, carboxylate group, amino group, phenol group, thiol group;

[0330] Alkoxy and hydroxyl groups, alcoholate groups, amino groups; and so on.

[0331] The polar groups of component (I) and component (II) through which these "polar groups" are bonded can be arbitrarily selected.

[0332] Here, regarding component (II) as a resin having a "polar group", for example, acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); polyvinyl acetate resin and its hydrolyzate; polymers of acrylic acid and its esters or amides; polyacetal resin; polyacrylate resin; polymers of acrylonitrile and / or methacrylonitrile, nitrile resins which are copolymers of these acrylonitrile monomers with other copolymerizable monomers containing 50% by weight or more; and the like.

[0333] As component (II), polyamide resin can also be mentioned.

[0334] Examples of the polyamide resin include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polybutylene adipamide (nylon 46), polybutylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polydecamethylene adipamide (nylon 106), polydecamethylene dodecanoamide (nylon 1010), polydecamethylene dodecanoamide (nylon 1012), polyundecanamide (nylon 11), and polydodecanoamide (nylon 12). 2) Polycaprolactam / polyhexamethylene adipamide copolymer (nylon 6 / 66) ( / indicates copolymer. Same as below), polycaprolactam / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaprolactam copolymer (nylon 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6 T / 6I), polyhexamethylene terephthalamide / polyundecanamide copolymer (nylon 6T / 11), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyxylylene sebacate (nylon XD10), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (nylon 6T / 5T), polyhexamethylene terephthalamide Polyamide resins (including copolymers thereof) such as polyamide / poly2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polypentamethylene terephthalamide / polydecanediamine copolymer (nylon 5T / 10T), polynonane terephthalamide (nylon 9T), polydecanediamine (nylon 10T), polydecanediamine / polyhexamethylene dodecanoyldiamine copolymer (nylon 10T / 612), polydecanediamine / polyhexamethylene adipamide copolymer (nylon 10T / 66), and polydodecanediamine (nylon 12T).

[0335] In addition, as component (II), for example, polyester resins, polyurethane resins, polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyethersulfone or polyallylsulfone; polyoxymethylene resins; polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly-4,4'-diphenylene sulfide; epoxy resins; polysulfone resins; phenol resins; polyarylate resins; polyetherketone polymers or copolymers; polyketone resins; fluorine resins; polyethylene terephthalate resins; polyoxybenzoyl polymers, polyimide resins; and the like.

[0336] From the perspective of high rigidity, component (II) is preferably a polyamide resin, an acrylic resin, a polyacetal resin, a polycarbonate resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyphenylene sulfide resin, a polysulfone resin, an epoxy resin, or a phenol resin, more preferably a polyamide resin, an epoxy resin, or a polyester resin, further preferably a polyamide resin from the perspective of processability, and even more preferably polycaprolactam (nylon 6) from the perspective of being processable at low temperatures.

[0337] When a polyamide resin is used as component (II), the ratio of the amine terminal to the carboxylic acid terminal in the terminals of the polyamide resin is preferably amine terminal / carboxylic acid terminal = 10 / 90 to 60 / 40, more preferably 20 / 80 to 55 / 45, from the perspective of compatibility with component (I).

[0338] Component (II) may be used alone or in combination of two or more.

[0339] From the viewpoint of processability and strength, the number average molecular weight of component (II) is usually 1000 or more, preferably 5000 or more, and more preferably 1×10 4 The upper limit is preferably 500×10 4 less than 100×10 4 the following.

[0340] In the resin composition of the present embodiment, the mass ratio of the component (I) to the component (II) is (I) / (II)=1 / 99 to 70 / 30.

[0341] By setting the mass ratio of component (I) to component (II) within the above numerical range, a resin composition having high strength and fully exhibiting impact resistance and toughness under ultralow temperature conditions can be obtained.

[0342] The preferred lower limit of the mass ratio of component (I) / component (II) is 5 / 95, more preferably 10 / 90, even more preferably 15 / 85, and even more preferably 20 / 80, and the preferred upper limit is 65 / 35, and even more preferably 40 / 60.

[0343] (Component (III))

[0344] The resin composition of the present embodiment may further contain a filler, a flame retardant, and other additives as component (III).

[0345] The component (III) is not particularly limited as long as it is a component generally used in compounding a resin composition.

[0346] Examples of fillers for component (III) include, but are not limited to, inorganic fillers such as silicon oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, hollow glass spheres, glass flakes, graphite, titanium oxide, potassium titanate whiskers, carbon fibers, aluminum oxide, kaolin, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconium oxide, potassium titanate, aluminum oxide, and metal particles; and organic fillers such as wood chips, wood powder, pulp, and cellulose nanofibers.

[0347] These fillers may be used alone or in combination of plural types.

[0348] The shapes of these fillers are not particularly limited and may be any of flaky, spherical, granular, powdery, and amorphous shapes.

[0349] Examples of flame retardants include halogen flame retardants such as bromine compounds, phosphorus flame retardants such as aromatic compounds, and inorganic flame retardants mainly composed of metal hydroxides. Inorganic flame retardants are preferred from the perspective of reducing environmental load.

[0350] Examples of inorganic flame retardants include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; metal oxides such as zinc borate and barium borate; calcium carbonate; clay; basic magnesium carbonate; and hydrous metal compounds such as hydrotalcite. In this embodiment, metal hydroxides such as magnesium hydroxide are preferred among these flame retardants for improving flame retardancy. These flame retardants also include so-called flame retardant adjuvants, which, while exhibiting low flame retardancy on their own, can synergistically exhibit superior effects when used in combination with other flame retardants.

[0351] Fillers and flame retardants that have been surface-treated in advance with a surface treatment agent such as a silane coupling agent may be used.

[0352] Other additives are not particularly limited as long as they are commonly used in the compounding of thermoplastic resins. Examples of such other additives include, but are not limited to, pigments and / or colorants such as carbon black and titanium oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide; release agents; plasticizers such as organopolysiloxanes, phthalate esters, adipate compounds, and azelate compounds, and mineral oils; antioxidants such as hindered phenol-based and phosphorus-based heat stabilizers; various stabilizers such as hindered amine-based light stabilizers; benzotriazole-based ultraviolet absorbers; antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; other additives, or mixtures thereof.

[0353] The resin composition of the present embodiment particularly preferably contains at least one stabilizer as the component (III).

[0354] Since the "resin (II) having a polar group" constituting the resin composition of the present embodiment has a polar group, its melting temperature is high from the viewpoints of entropy and enthalpy.

[0355] Furthermore, as described above, component (I) has a polar group bonded thereto. When the polar group is bonded by melt kneading, it melts at high temperatures and undergoes shear. Therefore, when exposed to these high temperatures, side reactions such as crosslinking occur, resulting in increased rigidity and a higher tan δ peak temperature. This may result in insufficient impact resistance and toughness under ultra-low temperature conditions.

[0356] That is, the tan δ peak temperature tends to shift to a higher temperature side due to side reactions such as crosslinking during modification. Therefore, by including a stabilizer as component (III) in the resin composition of this embodiment, the increase in the tan δ peak temperature can be suppressed.

[0357] The amount of the stabilizer added is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to component (I).

[0358] As the type of stabilizer, from the perspective of suppressing the above-mentioned side reactions such as crosslinking, preferably, phenol-based and amine-based stabilizers that react with carbon radicals generated by thermal decomposition of the modified block copolymer (I) and / or peroxide radicals generated by oxidation, and phosphorus-based and sulfur-based stabilizers that react with hydrogen peroxide are preferred. From the perspective of improving the reactivity with peroxide radicals and / or hydrogen peroxide, compounds further containing an aromatic ring are more preferred, and phenol-based, amine-based, and phosphorus-based stabilizers containing an aromatic ring are even more preferred.

[0359] As the stabilizer, conventionally known stabilizers can be used. Although not limited to the following, examples of phenolic stabilizers include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,1-dimethylpropyl)phenyl]]-1-yl acrylate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-dimethyl-2, 2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diylbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(ethylene oxide)], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0360] Examples of the amine system include 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, N,N″-diphenyl-1,4-phenylenediamine, N-phenyl-1-naphthylamine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, 4-isopropylaminodiphenylamine, N-(1,3-dimethylbutyl)-N′-phenyl-1,4-phenylenediamine, N,N′-di-sec-butyl-1,4-phenylenediamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.

[0361] Examples of the phosphorus-based phosphite include tris(2,4-di-tert-butylphenyl) phosphite, tri-p-cresyl phosphite, trihexyl phosphite, tributyl phosphite, tri-o-cresyl phosphite, tris(2-ethylhexyl) phosphite, trioctyl phosphite, and triisodecyl phosphite.

[0362] Examples of the sulfur-based compounds include didodecyl 3,3'-thiodipropionate, 3,3'-thiodipropionic acid, and 2-mercaptobenzimidazole.

[0363] These stabilizers may be used alone or in combination of two or more. From the perspective of achieving a b value of 30 or less when measuring a sheet having a thickness of 2 mm obtained by compression molding component (I) using a colorimeter, it is preferred to use a phenolic stabilizer in combination with a phosphorus stabilizer or a sulfur stabilizer.

[0364] The timing of adding the stabilizer to the resin composition of the present embodiment is not particularly limited. Since the stabilizer is expected to have the function of suppressing the generation of coloring components in the modification step based on melt kneading, it is preferable to add the stabilizer having an antioxidant function before the melt kneading step.

[0365] Specifically, examples include the pre-stage of the step of separating the copolymer from the solution after the polymerization reaction and hydrogenation reaction of component (I), and / or the pre-stage of the modification step of imparting polar groups to the polymer in the above-mentioned melt kneading method, and / or the pre-stage of the step of mixing component (I) and component (II).

[0366] (Ingredient (V))

[0367] The resin composition of the present embodiment may further contain, as component (V), 100 parts by mass or less of a block copolymer (V) relative to 100 parts by mass of component (I) in the resin composition of the present embodiment, within a range that does not impair the toughness and impact resistance under ultra-low temperature conditions. The block copolymer (V) is a block copolymer having a polymer block (A') mainly composed of vinyl aromatic compound units and a polymer block (B') mainly composed of conjugated diene compound units, and having no polar group bonded thereto, and satisfies the following conditions (vii) to (ix).

[0368] When it is preferable to reduce the viscosity of the resin composition in order to obtain a large-sized molded article using the resin composition of this embodiment, it is preferable to reduce the reactivity of component (II) and component (I). Therefore, component (V) preferably has no polar group bonded thereto.

[0369] Furthermore, in order not to impair the impact resistance and toughness under ultra-low temperature conditions, it is preferable to satisfy the following conditions (vii) to (ix).

[0370] <Condition (vii)>

[0371] The content of the vinyl aromatic compound unit in the block copolymer (V) is 1 to 30% by mass.

[0372] <Condition (viii)>

[0373] The polymer block (B') of the block copolymer (V) comprises units (a') derived from 1,2-bonds and / or 3,4-bonds and units (b') derived from 1,4-bonds. When the total content of the polymer block (B') is 100%, the content of the units (a') derived from 1,2-bonds and / or 3,4-bonds is 1 to 55%.

[0374] <Condition (ix)>

[0375] The polymer block (B') comprises an alkenyl monomer unit (a'1) obtained by hydrogenating the unit (a') derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b'1) obtained by hydrogenating the unit (b') derived from a 1,4-bond. When the total content of the polymer block (B') is 100%, the total content of the alkenyl monomer unit (a'1) and the alkenyl monomer unit (b'1) is 5 to 55%.

[0376] Furthermore, the block copolymer (V) more preferably satisfies the following condition (x).

[0377] <Condition(x)>

[0378] When the amount of the units (a') derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B') is 100%, the amount of the ethylenic monomer units (a'1) obtained by hydrogenating the units (a') derived from 1,2-bonds and / or 3,4-bonds is 80% or more.

[0379] When reducing the viscosity of the resin composition of the present embodiment, it is preferable to reduce the reactivity of the polar group of the component (II) with the component (I), as described above.

[0380] From the same perspective, when the resin composition of the present embodiment further contains component (V), component (V) preferably does not have a polar group bonded thereto. From the perspective of not impairing impact resistance and toughness under ultra-low temperature conditions, component (V) preferably satisfies the above-mentioned conditions (vii) to (ix), and more preferably satisfies condition (x), similarly to component (I), in order to ensure that the impact resistance and toughness under ultra-low temperature conditions are not impaired.

[0381] By satisfying the above conditions (vii) to (x), components (I) and (V) are in a low-rigidity rubbery state under ultralow temperature conditions. Therefore, the resin composition of this embodiment tends to have excellent impact resistance and toughness under ultralow temperature conditions.

[0382] The amount of component (V) added is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of component (I) in the resin composition of the present embodiment.

[0383] [Method for producing resin composition]

[0384] The method for producing the resin composition of the present embodiment is not particularly limited, and a known method can be used.

[0385] As a method for producing the resin composition of the present embodiment, for example, there can be mentioned a method of producing the resin composition using a known kneading device that can uniformly mix the respective resin components.

[0386] The kneading device can be used without particular limitation, and examples of the kneading device include a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, and a roll.

[0387] The melt-kneading temperature is preferably 100 to 400°C, more preferably 150 to 350°C.

[0388] For example, dry mixing can also be carried out using various mixers, and a melt kneading method using a common mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a kneader, a multi-screw extruder, or a roll can be used; a method in which the components are dissolved or dispersed and mixed, and then the solvent is removed by heating, etc.

[0389] In the production of the resin composition of the present embodiment, a melt mixing method using an extruder is preferred from the viewpoints of productivity and good kneading properties.

[0390] The shape of the obtained resin composition is not particularly limited, and examples thereof include pellets, sheets, strands, chips, etc. Alternatively, the composition may be directly formed into a molded article after melt kneading.

[0391] [Molding]

[0392] The molded body of this embodiment is a molded body of the resin composition of the above-mentioned embodiment. By processing and / or molding the resin composition of this embodiment, various molded bodies such as injection molded products, hollow molded products, compressed air molded products, vacuum molded products, extruded molded products, and pressed molded products in various shapes such as sheets, films, various containers, cylindrical containers, shells, and piping for use in ultra-low temperature environments can be obtained.

[0393] (Preferred embodiment of molded article)

[0394] The molded article of the present embodiment is particularly a molded article of a resin composition containing the following components:

[0395] At least one resin selected from the group consisting of polyamide resins, acrylic resins, polyacetal resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, epoxy resins, and phenol resins; and

[0396] A block copolymer having a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, wherein:

[0397] The block copolymer is a modified block copolymer, wherein the content of the vinyl aromatic compound unit is 1 to 30% by mass, the vinyl bond content in the polymer block (B) mainly composed of the conjugated diene compound unit is 1 to 55%, and the block copolymer has at least one selected from the group consisting of anhydride groups, carboxylic acid groups, and hydroxyl groups.

[0398] From the viewpoint of achieving excellent impact resistance and toughness in applications under ultralow temperature conditions, the molded article preferably satisfies the following conditions (I-1) to (II-1).

[0399] <Condition (I-1)>

[0400] The elongated test piece having a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the molded article had a tensile elongation at break of 15% or more at a tensile speed of 5 mm / min at -50°C.

[0401] <Condition (II-1)>

[0402] A strip test piece having a width of 10 mm, a length of 40 mm, and a thickness of 2 mm obtained from the molded article showed a peak at -60°C or lower in the viscoelasticity measurement under the conditions of a strain of 0.1% and a frequency of 1 Hz.

[0403] In the molded article, the hydrogenation rate of the conjugated diene compound unit in the modified block copolymer is preferably 5 to 55%. By setting the hydrogenation rate to 55% or less, the main dispersion peak temperature of the tan δ curve of the modified block copolymer can be set to -55°C or less.

[0404] Furthermore, excellent thermal stability can be obtained by setting the hydrogenation rate to 5% or more. The hydrogenation rate is more preferably 5 to 50%, further preferably 10 to 45%, and even more preferably 15 to 40%.

[0405] The hydrogenation rate can be controlled within the above numerical range by appropriately adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, etc. in the hydrogenation step.

[0406] The shape of the above-mentioned molded body is not particularly limited and can be processed into a known shape. For example, a test piece can be cut out from a portion of the molded body that is close to a plane to produce a dumbbell-shaped test piece or a long strip test piece. The test piece does not have to be flat, as long as it is flat to the extent that it can be measured for elongation at break and viscoelasticity. For example, if it is a cylindrical molded body, although it depends on the barrel diameter, it is easy to produce a test piece that can be measured by cutting out the test piece along the length direction. In addition, the thickness of the molded body can be thicker than 2mm. In this case, a file or the like can be used to cut off a portion with a thickness of more than 2mm, and the elongation at break and viscoelasticity can be measured using a test piece that is as flat as possible and set to a thickness of 2mm.

[0407] In the above molded article, a notched strip test piece having a width of 10 mm, a length of 80 mm, a thickness of 2 mm, and a notch shape obtained from the molded article is subjected to a Charpy impact test at -50°C with the impact direction being the side in accordance with JIS K 7111-1, and the Charpy impact value is preferably 10 kJ / m 2 As a result, excellent impact resistance can be obtained under ultra-low temperature conditions.

[0408] In the molded body of this embodiment, from the perspective of obtaining excellent properties under ultra-low temperature conditions, the modified block copolymer is preferably dispersed in a polar resin such as polyamide. In the dispersed state of the modified block copolymer in the above resin, the average dispersed particle size of the modified block copolymer is preferably less than 5 μm, more preferably less than 4 μm, and further preferably less than 3 μm.

[0409] The molded article is cut by cryosectioning, and the resulting cross-section is observed using a scanning electron microscope. The average particle size of the modified block copolymer dispersed in the molded article can be calculated from the resulting reflected electron image. Specifically, the resulting reflected electron image is binarized using image analysis software (imageJ), and the equivalent circle diameters of 500 or more island phases in the binarized image are calculated to obtain the average particle size.

[0410] The resin composition constituting the molded body may contain 1 to 50 parts by mass of fillers and other additives, more preferably 5 to 30 parts by mass of fillers, for the purpose of improving strength, relative to 100 parts by mass of the resin composition. Furthermore, in addition to toughness and impact resistance in ultra-low temperature environments, other additives such as flame retardants may be contained in an amount of 1 to 70 parts by mass relative to 100 parts by mass of the resin composition in order to provide additional functions such as flame retardancy and tracking resistance. When these additives are contained, the tensile elongation at break measured under the above conditions is preferably 10% or more, and the impact resistance is preferably 10 kJ / m 2 above.

[0411] The molded article can be formed into any shape according to the intended use, and examples thereof include, but are not limited to, various containers, cylindrical containers, and shells.

[0412] In particular, when strength is required in the intended use, the resin combined with the modified block copolymer is preferably a polyamide resin, polyphenylene sulfide resin, polysulfone resin, or epoxy resin. When appearance is required, polyamide resin, acrylic resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, or polybutylene terephthalate resin is preferred. When airtightness is particularly required, polyamide resin, acrylic resin, epoxy resin, and phenol resin are preferred. When strength and processability are required in addition to airtightness, polyamide resin is preferred. From the perspective of cost, polyhexamethylene adipamide (nylon 66) and polycaprolactam (nylon 6) are particularly preferred.

[0413] Example

[0414] The present embodiment will be described in detail below with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples.

[0415] Incidentally, the structure identification and physical property measurement of the modified block copolymer (component (I)) used in the following Examples and Comparative Examples were performed as follows.

[0416] [Methods for determining the structure and physical properties of polymers]

[0417] ((1) Content of vinyl aromatic compound units in block copolymer)

[0418] The block copolymer before modification and hydrogenation was used for measurement using an ultraviolet spectrophotometer (UV-2450 manufactured by Shimadzu Corporation), and the measured value was defined as the content of the vinyl aromatic compound unit in the modified block copolymer (I).

[0419] ((2) Vinyl bond content of block copolymer)

[0420] The block copolymer before modification and hydrogenation was measured using an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-230). The vinyl bond content of the block copolymer was calculated by the Hampton method. This value was taken as the content of the unit (a) derived from 1,2-bonds and / or 3,4-bonds, assuming that the polymer block (B) of the modified block copolymer (I) was 100%.

[0421] ((3) Molecular weight and molecular weight distribution of block copolymers)

[0422] The molecular weight of the block copolymer before modification and hydrogenation was measured by GPC [apparatus: LC-10 (manufactured by Shimadzu Corporation), column: TSKgel GMHXL (4.6 mm×30 cm)].

[0423] Tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35°C.

[0424] The molecular weight is a weight average molecular weight obtained by determining the peak molecular weight of the chromatogram using a calibration curve determined by measurement of commercially available standard polystyrene (created using the peak molecular weight of the standard polystyrene).

[0425] It should be noted that when there are multiple peaks in the chromatogram, the molecular weight is the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (derived from the area ratio of each peak in the chromatogram). In addition, the molecular weight distribution is the ratio (Mw / Mn) of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0426] ((4) Double bond hydrogenation ratio of the conjugated diene monomer unit in the block copolymer (vinyl hydrogenation ratio))

[0427] The hydrogenated modified block copolymer was used to measure the hydrogenation rate of the double bonds in the conjugated diene monomer units using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUKER).

[0428] ((5) tanδ peak temperature)

[0429] First, a block copolymer before modification and hydrogenation and a modified block copolymer after modification and hydrogenation were used as samples. These samples were cut into sheet-shaped molded bodies with a size of 10 mm in width and 40 mm in length to serve as measurement samples.

[0430] Next, the measurement sample was placed in the twisting layout of the ARES apparatus (trade name, manufactured by TA Instruments Co., Ltd.) and viscoelasticity was measured under the conditions of effective measurement length 25 mm, strain 0.3%, frequency 1 Hz, and heating rate 3°C / min.

[0431] The tan δ peak temperature was determined as a value obtained from a peak detected by automatic measurement using RSI Orchestrator (trade name, manufactured by TA Instruments).

[0432] ((6) Determination of Residual Metal Amount)

[0433] The metal content in the block copolymer was determined by elemental analysis using inductively coupled plasma (ICP, ICPS-7510, Shimadzu Corporation) to measure the amounts of Ti and Li remaining from the polymerization initiator used and the catalyst species in the hydrogenation reaction.

[0434] Regarding the metal amount, it is preferable that the total amount of the above-mentioned metals is 120 ppm or less.

[0435] ((6) Determination of b value)

[0436] The modified block copolymer (I) described later was compression-molded to prepare a sheet having a thickness of 2 mm, which was used as a measurement sample.

[0437] The b value of the sheet was measured using a colorimeter (ZE-2000 manufactured by Nippon Denshoku Industries, Ltd.).

[0438] ((7) Measurement of resin temperature)

[0439] A temperature sensor (T-270Z manufactured by Rikaku Kogyo Co., Ltd.) was inserted into the die portion of the extruder to measure the temperature of the modified block copolymer (I) described later.

[0440] ((8) Determination of the amount of cross-linking components)

[0441] 5 g of the modified block copolymer (I) described below was dissolved in 200 mL of toluene and filtered with suction through a mass-measured filter paper (thickness 0.2 mm, maximum diameter 6 μm, collection efficiency 65%). The filter paper was thoroughly dried, its mass was measured, and the amount of crosslinked components was calculated by subtracting the mass of the filter paper before filtration.

[0442] [Preparation of hydrogenation catalyst]

[0443] In the Examples and Comparative Examples described below, the hydrogenation catalyst used in producing the hydrogenated block copolymer was prepared by the following method.

[0444] A reaction container equipped with a stirrer was purged with nitrogen, and 1 liter of dried and purified cyclohexane was added thereto.

[0445] Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While the mixture was thoroughly stirred, a n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for about 3 days. This yielded a hydrogenation catalyst.

[0446] [Hydrogenated block copolymer]

[0447] Hydrogenated block copolymers of a vinyl aromatic compound and a conjugated diene (1) to (28) were prepared as follows.

[0448] The structure of the obtained hydrogenated block copolymer block, the content of the vinyl aromatic compound unit, the vinyl bond amount, the hydrogenation ratio, the vinyl hydrogenation ratio, the heavy metal content, and the tan δ peak temperature obtained from the viscoelastic spectrum are shown in Tables 1 to 3 below.

[0449] [Amount of stabilizer added]

[0450] It is found that the amount of the stabilizer added is preferably 6 parts by mass or less, more preferably 5 parts by mass or less, further preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the hydrogenated block copolymer (I).

[0451] (Hydrogenated block copolymer (1))

[0452] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0453] First, a cyclohexane solution containing 7.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0454] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0455] Next, a cyclohexane solution containing 85 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0456] Then, a cyclohexane solution containing 7.5 parts by mass of styrene (concentration: 20% by mass) was added, and then methanol was added to terminate the polymerization reaction, thereby obtaining a block copolymer.

[0457] The block copolymer obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.8×10 4 , the molecular weight distribution was 1.10, and the content of the unit (a) derived from 1,2-bond and / or 3,4-bond (vinyl bond amount (%): unit (a) / block (B)) was 22%.

[0458] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours.

[0459] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer to obtain a hydrogenated block copolymer (1).

[0460] When the total content of the polymer block (B) of the obtained hydrogenated block copolymer (1) is 100%, the total ratio of the olefinic monomer units (a1) obtained by hydrogenating the above-mentioned units (a) and the olefinic monomer units (b1) obtained by hydrogenating the above-mentioned units (b) (hydrogenation ratio: (a1) + (b1) / (B)) is 32%, and the ratio of the units (a1) to the units (a) (vinyl hydrogenation ratio: (a1) / (a)) is 95%.

[0461] (Hydrogenated block copolymer (2))

[0462] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (1) except that 0.4 mol of TMEDA was added to 1 mol of n-butyllithium and the hydrogenation reaction time was set to 0.75 hours.

[0463] The hydrogenated block copolymer (2) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.0×10 4 , molecular weight distribution is 1.10, vinyl bond content is 45%, hydrogenation rate is 40%, and vinyl hydrogenation rate is 83%.

[0464] (Hydrogenated block copolymer (3))

[0465] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above-mentioned hydrogenated block copolymer (1) except that the hydrogenation reaction time was changed to 1.25 hours.

[0466] The hydrogenated block copolymer (3) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, vinyl bond content is 19%, hydrogenation rate is 45%, and vinyl hydrogenation rate is 99%.

[0467] (Hydrogenated block copolymer (4))

[0468] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (1) except that 0.1 mol of TMEDA was added relative to 1 mol of n-butyllithium.

[0469] The hydrogenated block copolymer (4) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.1×10 4, molecular weight distribution is 1.10, vinyl bond content is 12%, hydrogenation rate is 34%, and vinyl hydrogenation rate is 99%.

[0470] (Hydrogenated block copolymer (5))

[0471] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above-mentioned hydrogenated block copolymer (1) except that the hydrogenation reaction time was changed to 0.25 hours.

[0472] The hydrogenated block copolymer (5) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 9.9×10 4 , molecular weight distribution is 1.10, vinyl bond content is 24%, hydrogenation rate is 26%, and vinyl hydrogenation rate is 86%.

[0473] (Hydrogenated block copolymer (6))

[0474] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0475] First, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0476] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0477] Then, a cyclohexane solution containing 75 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0478] Then, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added, and then methanol was added to terminate the polymerization reaction.

[0479] The block copolymer obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, and vinyl bond content is 23%.

[0480] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours.

[0481] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer (6).

[0482] The obtained hydrogenated block copolymer (6) had a hydrogenation rate of 30% and a vinyl hydrogenation rate of 89%.

[0483] (Hydrogenated block copolymer (7))

[0484] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0485] First, a cyclohexane solution containing 5 parts by mass of styrene (concentration: 20% by mass) was added.

[0486] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0487] Then, a cyclohexane solution containing 90 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0488] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration: 20% by mass) was added.

[0489] Methanol was then added to stop the polymerization reaction.

[0490] The block copolymer obtained as described above has a styrene content of 10% by mass and a weight average molecular weight of 10.5×10 4 , molecular weight distribution is 1.10, and vinyl bond content is 24%.

[0491] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours.

[0492] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer to obtain a hydrogenated block copolymer (7).

[0493] The obtained hydrogenated block copolymer (7) had a hydrogenation rate of 36% and a vinyl hydrogenation rate of 95%.

[0494] (Hydrogenated block copolymer (8))

[0495] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0496] First, a cyclohexane solution containing 5 parts by mass of butadiene (concentration: 20% by mass) was added.

[0497] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 3 minutes.

[0498] Then, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.

[0499] Then, a cyclohexane solution containing 70 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 40 minutes.

[0500] Then, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes. Methanol was then added to terminate the polymerization reaction.

[0501] The block copolymer obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.5×10 4 , molecular weight distribution is 1.10, and vinyl bond content is 30%.

[0502] The hydrogenation catalyst prepared above was further added to the obtained block copolymer at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and hydrogenation was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours to obtain a hydrogenated block copolymer.

[0503] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer to obtain a hydrogenated block copolymer (8).

[0504] The obtained hydrogenated block copolymer (8) had a hydrogenation rate of 40% and a vinyl hydrogenation rate of 96%.

[0505] (Hydrogenated block copolymer (9))

[0506] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0507] First, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was added.

[0508] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0509] Then, a cyclohexane solution containing 80 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0510] Next, 0.27% of ethyl benzoate was added relative to 1 mol of n-butyl lithium, and the mixture was reacted at 70° C. for 20 minutes.

[0511] The block copolymer obtained as described above has a styrene content of 20% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, coupling rate is 49%, and vinyl bond content is 18%.

[0512] The hydrogenation catalyst prepared above was further added to the obtained block copolymer at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and hydrogenation was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours to obtain a hydrogenated block copolymer.

[0513] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer to obtain a hydrogenated block copolymer (9).

[0514] The obtained hydrogenated block copolymer (9) had a hydrogenation rate of 25% and a vinyl hydrogenation rate of 95%.

[0515] (Hydrogenated block copolymer (10))

[0516] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (1) except that 0.16 parts by mass of n-butyl lithium was added based on 100 parts by mass of all monomers.

[0517] The hydrogenated block copolymer (10) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 6.8×10 4 , molecular weight distribution is 1.10, vinyl bond content is 24%, hydrogenation rate is 33%, and vinyl hydrogenation rate is 97%.

[0518] (Hydrogenated block copolymer (11))

[0519] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (1) except that 0.09 parts by mass of n-butyl lithium was added based on 100 parts by mass of all monomers.

[0520] The block copolymer (10) obtained as described above has a styrene content of 15% by mass and a weight average molecular weight of 12.5×10 4, molecular weight distribution is 1.10, vinyl bond content is 19%, hydrogenation rate is 30%, and vinyl hydrogenation rate is 98%.

[0521] (Hydrogenated block copolymer (12))

[0522] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0523] First, a cyclohexane solution containing 17.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0524] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0525] Then, a cyclohexane solution containing 65 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0526] Then, a cyclohexane solution containing 17.5 parts by mass of styrene (concentration: 20% by mass) was added, and then methanol was added to terminate the polymerization reaction.

[0527] The block copolymer obtained as described above has a styrene content of 10% by mass and a weight average molecular weight of 10.5×10 4 , molecular weight distribution is 1.10, and vinyl bond content is 24%.

[0528] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 0.5 hours.

[0529] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the copolymer to obtain a hydrogenated block copolymer (12).

[0530] The obtained hydrogenated block copolymer (12) had a hydrogenation rate of 32% and a vinyl hydrogenation rate of 95%.

[0531] (Hydrogenated polymer block (13))

[0532] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above-mentioned hydrogenated block copolymer (1) except that the hydrogenation reaction time was changed to 1.75 hours.

[0533] The hydrogenated block copolymer (13) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.3×104 , molecular weight distribution is 1.10, vinyl bond content is 26%, hydrogenation rate is 68%, and vinyl hydrogenation rate is 99%.

[0534] (Hydrogenated polymer block (14))

[0535] Polymerization and hydrogenation were carried out in the same manner as in the hydrogenated block copolymer (1), except that 0.25 mol of TMEDA was added per mol of n-butyllithium and the hydrogenation reaction was carried out for 2 hours at a hydrogenation temperature of 50°C.

[0536] The hydrogenated block copolymer (14) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, vinyl bond content is 35%, hydrogenation rate is 57%, and vinyl hydrogenation rate is 75%.

[0537] (Hydrogenated block copolymer (15))

[0538] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (1) except that 1 mol of TMEDA was added relative to 1 mol of n-butyllithium.

[0539] The hydrogenated block copolymer (15) obtained as described above had a styrene content of 15% by mass and a weight average molecular weight of 10.1×10 4 , molecular weight distribution is 1.10, vinyl bond content is 69%, hydrogenation rate is 40%, and vinyl hydrogenation rate is 50%.

[0540] (Hydrogenated block copolymer (16))

[0541] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0542] First, a cyclohexane solution containing 5 parts by mass of butadiene (concentration: 20% by mass) was added.

[0543] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 3 minutes.

[0544] Then, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.

[0545] Then, a cyclohexane solution containing 55 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 40 minutes.

[0546] Then, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes. Methanol was then added to terminate the polymerization reaction.

[0547] The block copolymer obtained as described above has a styrene content of 40% by mass and a weight average molecular weight of 10.2×10 4 , molecular weight distribution is 1.10, and vinyl bond content is 34%.

[0548] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70° C. for about 0.5 hours.

[0549] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer to obtain a hydrogenated block copolymer (16).

[0550] The obtained hydrogenated block copolymer (16) had a hydrogenation rate of 25% and a vinyl hydrogenation rate of 58%.

[0551] (Hydrogenated block copolymer (17))

[0552] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above-mentioned hydrogenated block copolymer (6), except that the amount of TMEDA added was 0.38 mol relative to 1 mol of n-butyllithium, 150 ppm of hydrogenation catalyst was added based on Ti per 100 parts by mass of the block copolymer, and the hydrogenation reaction time was 0.5 hour.

[0553] The hydrogenated block copolymer (17) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.7×10 4 , molecular weight distribution is 1.10, vinyl bond content is 40%, hydrogenation rate is 44%, and vinyl hydrogenation rate is 81%.

[0554] (Hydrogenated block copolymer (18))

[0555] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above-mentioned hydrogenated block copolymer (17), except that 100 ppm of a hydrogenation catalyst was added based on Ti per 100 parts by mass of the block copolymer and 2.5 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer per 100 parts by mass of the hydrogenated block copolymer.

[0556] The hydrogenated block copolymer (18) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.6×10 4 , molecular weight distribution is 1.10, vinyl bond content is 39%, hydrogenation rate is 45%, and vinyl hydrogenation rate is 82%.

[0557] (Hydrogenated block copolymer (19))

[0558] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the above hydrogenated block copolymer (18) except that 2.5 parts by mass of 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer.

[0559] The hydrogenated block copolymer (19) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, vinyl bond content is 39%, hydrogenation rate is 44%, and vinyl hydrogenation rate is 81%.

[0560] (Hydrogenated block copolymer (20))

[0561] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (18) except that 2.5 parts by mass of 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,1-dimethylpropyl)phenyl]]-1-ylacrylate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer.

[0562] The hydrogenated block copolymer (20) obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.6×10 4 , molecular weight distribution is 1.11, vinyl bond content is 41%, hydrogenation rate is 45%, and vinyl hydrogenation rate is 81%.

[0563] (Hydrogenated block copolymer (21))

[0564] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (18) except that 2.5 parts by mass of 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,1-dimethylpropyl)phenyl]]-1-ylacrylate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer.

[0565] The hydrogenated block copolymer (21) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.6×10 4, molecular weight distribution is 1.11, vinyl bond content is 40%, hydrogenation rate is 45%, and vinyl hydrogenation rate is 83%.

[0566] (Hydrogenated block copolymer (22))

[0567] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (18) except that 2.5 parts by mass of tris(2,4-di-tert-butylphenyl) phosphite was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer.

[0568] The hydrogenated block copolymer (22) obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.5×10 4 , molecular weight distribution is 1.10, vinyl bond content is 40%, hydrogenation rate is 44%, and vinyl hydrogenation rate is 82%.

[0569] (Hydrogenated block copolymer (23))

[0570] The polymerization reaction and hydrogenation reaction were carried out in the same manner as in the hydrogenated block copolymer (18) except that 2.5 parts by mass of didodecyl 3,3'-thiodipropionate was added as a stabilizer based on 100 parts by mass of the hydrogenated block copolymer.

[0571] The hydrogenated block copolymer (23) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.6×10 4 , molecular weight distribution is 1.11, vinyl bond content is 40%, hydrogenation rate is 44%, and vinyl hydrogenation rate is 81%.

[0572] (Hydrogenated block copolymer (24))

[0573] The polymerization reaction and hydrogenation reaction were carried out in the same manner as the hydrogenated block copolymer (6) except that the amount of TMEDA added was 0.38 mol relative to 1 mol of n-butyl lithium, and then a mixed solution of 30 parts by mass of water and sulfuric acid was added relative to 100 parts by mass of the hydrogenated block copolymer. It should be noted that the amount of sulfuric acid added was adjusted so that the pH of the water removed by the decanter in the subsequent process was 7.0. The solution was decanted to remove most of the water until the amount of water reached 3 parts by mass, and 0.4 mol of carbon dioxide was added and mixed relative to 1 mol of the metal of the initiator. Thereafter, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer. As described in the latter part of Japanese Patent Publication No. 05-54845, the solution was subjected to a stripping method and then mixed using a twin-screw extruder to remove the solvent.

[0574] The hydrogenated block copolymer (24) obtained as described above had a styrene content of 25% by mass and a weight average molecular weight of 10.7×10 4 , molecular weight distribution is 1.08, vinyl bond content is 40%, hydrogenation rate is 44%, and vinyl hydrogenation rate is 81%.

[0575] (Terminal amine-modified hydrogenated block copolymer (25))

[0576] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0577] First, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0578] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0579] Then, a cyclohexane solution containing 75 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0580] Next, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0581] Then, 1,3-dimethyl-2-imidazolidinone (hereinafter also referred to as "DMI") in an amount equivalent to 1 mol of n-butyllithium was added, and the mixture was reacted at 70° C. for 10 minutes. After the reaction was completed, methanol was added.

[0582] The terminal amine-modified block copolymer obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.4×10 4 , molecular weight distribution was 1.10, vinyl bond content was 44%, and modification rate was 0.06 mass %.

[0583] The hydrogenation catalyst prepared above was further added to the obtained block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 1.25 hours.

[0584] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the block copolymer to obtain a terminal amine-modified hydrogenated block copolymer (25). The obtained terminal amine-modified hydrogenated block copolymer (25) had a hydrogenation rate of 46% and a vinyl hydrogenation rate of 81%.

[0585] (Terminal amine-modified hydrogenated block copolymer (26))

[0586] The same operation as in the above (modified hydrogenated block copolymer (25)) was carried out except that the hydrogenation reaction was carried out for 1.75 hours.

[0587] The terminal-modified block copolymer (26) obtained as described above had a styrene content of 25% by mass and a weight-average molecular weight of 10.4×10 4 , molecular weight distribution is 1.10, vinyl bond content is 44%, modification rate is 0.06 mass%, hydrogenation rate is 67%, and vinyl hydrogenation rate is 98%.

[0588] (Terminal modified hydrogenated block copolymer (27))

[0589] Batch polymerization was carried out using a tank-type reactor (internal volume 10 L) equipped with a stirring device and a jacket.

[0590] First, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added.

[0591] Next, 0.11 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.

[0592] Then, a cyclohexane solution containing 75 parts by mass of butadiene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 45 minutes.

[0593] Then, a cyclohexane solution containing 12.5 parts by mass of styrene (concentration: 20% by mass) was added, and then an equimolar amount of ε-caprolactam relative to 1 mol of n-butyllithium was added, and the mixture was reacted at 70°C for 10 minutes.

[0594] The terminal modified block copolymer obtained as described above has a styrene content of 25% by mass and a weight average molecular weight of 10.5×10 4 , molecular weight distribution is 1.10, vinyl bond content is 45%, and modification rate is 0.05 mass %.

[0595] The hydrogenation catalyst prepared above was further added to the obtained terminal-modified block copolymer in an amount of 100 ppm based on Ti per 100 parts by mass of the terminal-modified block copolymer, and hydrogenation was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 1.25 hours.

[0596] Next, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer based on 100 parts by mass of the terminal-modified hydrogenated block copolymer to obtain a terminal-modified hydrogenated block copolymer (27).

[0597] The obtained terminal-modified hydrogenated block copolymer (27) had a hydrogenation rate of 45% and a vinyl hydrogenation rate of 80%.

[0598] (Terminal hydroxyl modified hydrogenated block copolymer (28))

[0599] The same operation as in the above (terminally modified hydrogenated block copolymer (27)) was carried out except that the hydrogenation reaction was carried out for 1.75 hours.

[0600] The terminal-modified hydrogenated block copolymer (28) obtained as described above has a styrene content of 25% by mass and a weight-average molecular weight of 10.4×10 4 , molecular weight distribution is 1.09, vinyl bond content is 44%, modification rate is 0.05 mass%, hydrogenation rate is 66%, and vinyl hydrogenation rate is 98%.

[0601]

[0602]

[0603] [Modified block copolymer]

[0604] A modified block copolymer constituting the resin composition described below was prepared as follows.

[0605] The temperature of the entire length of the extruder was set at 150° C. to 220° C., and compounding was performed using a twin-screw extruder.

[0606] The screw speed was 270 rpm and the extrusion rate was 5 kg / h.

[0607] The hydrogenated block copolymers (1) to (24) were mixed with maleic anhydride and then fed to a vented extruder.

[0608] In the following Table 4, in the modified block copolymer (1)-6, a mesh was inserted into the die portion of the extruder to reduce the crosslinking component.

[0609] The strands discharged from the extruder were pelletized and dried at about 60° C. for 3 hours.

[0610] Tables 4 to 7 show the amount of maleic anhydride added (assuming the block copolymer is 100 parts), the modification ratio, and the tan δ peak temperature obtained from the viscoelastic spectrum after modification.

[0611] Tables 4 to 7 show the numbers of the hydrogenated block copolymers used, and are described separately according to the modification conditions such as the blending amount of maleic anhydride.

[0612] Furthermore, productivity was evaluated as follows based on the frequency of screen replacement per hour during extrusion.

[0613] ○: 3 times / hour △: 10 times / hour ×: 15 times / hour

[0614] In the table, (a) indicates the amount (parts by mass) added relative to 100 parts by mass of the hydrogenated block copolymer, and (b) indicates the occurrence of gelation.

[0615] (c) indicates that analysis is not possible.

[0616]

[0617]

[0618] As shown in Tables 1 to 7, the amount of maleic anhydride in modified block copolymer (1)-4 exceeded the most preferred amount from the perspective of productivity. Therefore, controlling the resin temperature within the preferred temperature range resulted in a significant decrease in productivity. Furthermore, from the perspective of the b value, the amount of maleic anhydride added exceeded the preferred amount, resulting in a b value outside the range of condition (v).

[0619] On the other hand, in (24)-2, the amount of maleic anhydride added was the same as that in (1)-4, but since the amount of metal was small, the b value was within the range of condition (v).

[0620] In the hydrogenated block copolymer (15), the vinyl hydrogenation ratio was outside the range of the above-mentioned condition (iv), so the thermal stability was poor and gelation occurred due to the heat during modification.

[0621] In hydrogenated block copolymer (14), the vinyl hydrogenation ratio also fell outside the range of condition (iv) above. However, since the hydrogenation ratio was higher than that of hydrogenated block copolymer (15), modification could be performed without gelation. However, certain side reactions occurred, resulting in an increase in the tan δ peak temperature.

[0622] In the hydrogenated block copolymer (16), the vinyl hydrogenation ratio also fell outside the range of the aforementioned condition (iv). However, since the amount of the conjugated diene compound that undergoes side reactions was less than that of the hydrogenated block copolymer (15), modification was possible without gelation. However, certain side reactions occurred, resulting in an increase in the tan δ peak temperature.

[0623] In the hydrogenated block copolymer (17), the amount of heavy metal is outside the above-mentioned preferred range, and therefore the b value is outside the range of the above-mentioned condition (v).

[0624] In the hydrogenated block copolymers (18) to (23), the amount of the stabilizer is outside the above-mentioned most preferred range, and therefore the b value is outside the range of the above-mentioned condition (v).

[0625] [Component (II): Resin having a polar group (excluding component (I))]

[0626] The following commercially available products were used.

[0627] Polyamide resin: Leona 1300S (manufactured by Asahi Kasei Corporation),

[0628] Terminal amine concentration / carboxylic acid concentration = 22 / 78

[0629] UBE Nylon 1013B (manufactured by Ube Industries, Ltd.)

[0630] Terminal amine concentration / carboxylic acid concentration = 42 / 58

[0631] GF reinforced polyamide resin: 1300G

[0632] Ethylene vinyl alcohol (EVOH) resin: Soarnol E / ET

[0633] [Examples 1 to 37], [Comparative Examples 1 to 18]

[0634] The resin composition was prepared using the above components according to the following preparation method.

[0635] The composition ratio and physical properties are shown in the following table.

[0636] <Method for Preparing Resin Composition>

[0637] The temperature of the entire length of the extruder was set to 180 to 280° C., and the component (I) and the component (II) were compounded using a twin-screw extruder.

[0638] The screw rotation speed was about 270 rpm, and the extrusion rate was 5 kg / h.

[0639] Component (I) and component (II) are generally supplied from the throat of the extruder.

[0640] The strands discharged from the extruder were pelletized and dried for 3 hours at approximately 100° C. The dried pellets were injection molded into dumbbell-shaped test pieces A for physical property measurements described below.

[0641] <Methods for measuring physical properties of resin compositions>

[0642] ((1) Toughness)

[0643] Evaluation was performed by measuring elongation at break by a tensile test in accordance with ISO 527. The tensile speed was 5 mm / min and the measurement temperature was -50°C and -70°C.

[0644] ((2) Impact resistance)

[0645] The notched Charpy impact strength was measured and evaluated in accordance with JIS K 7111-1.

[0646] As for the test piece, both ends of the above-mentioned ISO dumbbell shape were cut, and the parallel portion was made into a long strip test piece with a length of about 80 mm, a width of about 10 mm, and a thickness of about 4 mm, with the notch shape being A and the striking direction being lateral.

[0647] The measurement temperature is -50°C and -70°C. The unit is kJ / m 2 .

[0648]

[0649] [Table 9]

[0650]

[0651] [Table 10]

[0652]

[0653] [Table 11]

[0654]

[0655]

[0656]

[0657] Compared with Comparative Examples 1 to 18, Examples 1 to 37 also exhibited excellent impact resistance under ultra-low temperature conditions.

[0658] In Comparative Examples 4 to 8, 12, 16, and 17, hydrogenated block copolymers (12) and (16) having an amount of vinyl aromatic compound outside the range of the present invention are used. Therefore, although they are in a rubbery state at ultra-low temperatures, their high rigidity results in poor impact resistance and toughness.

[0659] In addition, in the modified block copolymers (17) to (23), although the polymerization reaction and hydrogenation reaction were carried out under the same conditions as (12), since the stabilizer and metal amount were not in the most preferred range, the b value, impact resistance under ultra-low temperature conditions, and toughness were reduced.

[0660] Comparative Examples 9 to 11, 13, 14, and 18 use hydrogenated block copolymers (13) and (14) whose hydrogenation rates are outside the range of the present invention. Therefore, the tanδ peak temperature is on the high temperature side of the measurement temperature, and the copolymer is in a glassy state under ultra-low temperature conditions, resulting in poor impact resistance and toughness.

[0661] This application is based on Japanese Patent Application No. 2020-091932 filed with the Japan Patent Office on May 27, 2020, the contents of which are incorporated herein by reference.

[0662] Industrial Applicability

[0663] The resin composition of the present invention has industrial applicability as a material for molded articles, containers, and housings that are used at ultra-low temperatures or that may be exposed to ultra-low temperatures during use.

Claims

1. A resin composition comprising the following components: Component (I): a modified block copolymer (I) having a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, and having 0.01% by mass or more of polar groups; and Component (II): a resin (II) having a polar group other than the component (I), in, The mass ratio of the component (I) to the component (II) is (I) / (II)=1 / 99 to 70 / 30, The polar group of the component (I) is contained in the polymer block (B), In the component (I), when the polymer block (B) is present at the end of the modified block copolymer (I), the case where the polar group is bonded to the reaction product of a polymerization initiator having a functional group and the polymer block (B) at the end, and the conjugated diene compound unit of the polymer block (B) as the active end is excluded; and the case where the polar group is bonded to the polymer block (A) is excluded. The component (I) satisfies the following conditions (i) to (iii): <Condition (i)> The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 1% to 30% by mass; <Condition (ii)> The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds, and when the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1% to 55%; <Condition (iii)> The polymer block (B) comprises an alkenyl monomer unit (a1) formed by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an alkenyl monomer unit (b1) formed by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 5% to 55%.

2. The resin composition according to claim 1, wherein The component (I) further satisfies the following condition (iv), <Condition (iv)> When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

3. The resin composition according to claim 1 or 2, wherein The component (I) is a modified block copolymer having 0.01% to 5% by mass of polar groups.

4. The resin composition according to claim 1 or 2, wherein The component (II) is at least one selected from the group consisting of polyamide resins, acrylic resins, polyacetal resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, epoxy resins, and phenol resins.

5. The resin composition according to claim 1 or 2, comprising at least one stabilizer as component (III).

6. The resin composition according to claim 1 or 2, wherein The component (I) further satisfies the following condition (v), <Condition(v)> When a sheet having a thickness of 2 mm obtained by compression-molding the component (I) was measured using a colorimeter, the b value was 30 or less.

7. The resin composition according to claim 1 or 2, wherein The polar group of the component (I) is at least one selected from the group consisting of anhydride groups, carboxylic acid groups, and hydroxyl groups.

8. The resin composition according to claim 1 or 2, wherein The component (I) further satisfies the following condition (vi), <Condition (vi)> 5 g of the component (I) was dissolved in 200 mL of toluene and suction filtered using filter paper with a thickness of 0.2 mm, a maximum diameter of 6 μm, and a capture efficiency of 65%. The component on the filter paper, calculated from the mass difference between the filter paper after sufficient drying and the filter paper before filtration, was less than 0.3 g.

9. The resin composition according to claim 1 or 2, wherein The resin composition further comprises, as component (V), 100 parts by mass or less of a block copolymer (V) relative to 100 parts by mass of component (I) in the resin composition, wherein the block copolymer (V) is a block copolymer having a polymer block (A') mainly composed of a vinyl aromatic compound unit and a polymer block (B') mainly composed of a conjugated diene compound unit and having no polar group bonded thereto, and satisfies the following conditions (vii) to (ix), <Condition (vii)> The content of the vinyl aromatic compound unit in the block copolymer (V) is 1% to 30% by mass; <Condition (viii)> The polymer block (B') of the block copolymer (V) comprises units (a') derived from 1,2-bonds and / or 3,4-bonds and units (b') derived from 1,4-bonds, and when the total content of the polymer block (B') is 100%, the content of the units (a') derived from 1,2-bonds and / or 3,4-bonds is 1% to 55%; <Condition (ix)> The polymer block (B') comprises an alkenyl monomer unit (a'1) formed by hydrogenating the unit (a') derived from 1,2-bonding and / or 3,4-bonding and an alkenyl monomer unit (b'1) formed by hydrogenating the unit (b') derived from 1,4-bonding. When the total content of the polymer block (B') is 100%, the total content of the alkenyl monomer unit (a'1) and the alkenyl monomer unit (b'1) is 5% to 55%.

10. The resin composition according to claim 3, wherein The component (I) is a modified block copolymer having 0.05% by mass to 4% by mass of polar groups.

11. The resin composition according to claim 5, wherein The stabilizer is selected from the group consisting of phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers.

12. The resin composition according to claim 5, wherein The amount of the stabilizer added is 0.01% by mass to 3% by mass, based on 100% by mass of the component (I).

13. The resin composition according to claim 1 or 2, wherein The content of the vinyl aromatic compound unit in the modified block copolymer (I) is 5% by mass to 28% by mass.

14. The resin composition according to claim 1 or 2, wherein The main dispersion peak of the tan δ curve of the modified block copolymer (I) in the viscoelastic spectrum exists below -55°C.

15. The resin composition according to claim 1 or 2, wherein When the total content of the polymer block (B) is 100%, the content of the unit (a) is 10% to 50%.

16. The resin composition according to claim 1 or 2, wherein When the total content of the polymer block (B) is 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 15% to 50%.

17. The resin composition according to claim 1 or 2, wherein In the modified block copolymer (I), the residual metal amount of Ti, Li, Mg, Fe, and compounds containing these metals is 120 ppm or less.

18. The resin composition according to claim 1 or 2, wherein The weight average molecular weight of the modified block copolymer (I) is 1×10 4 ~5×10 5 .

19. The resin composition according to claim 1 or 2, wherein The molecular weight distribution of the modified block copolymer (I) is 1.04 or more and 4.0 or less.

20. The resin composition according to claim 1 or 2, wherein The mass ratio of the component (I) to the component (II) is (I) / (II)=10 / 90 to 40 / 60.

21. A method for producing a modified hydrogenated block copolymer, comprising the following steps: A process for producing a block copolymer comprising a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units, satisfying the following conditions (i) and (ii); a step of obtaining a hydrogenated block copolymer, wherein the block copolymer is hydrogenated in a manner satisfying the following conditions (iii) and (iv) to obtain a hydrogenated block copolymer; and The modification step is to subject the hydrogenated block copolymer to a modification reaction under melt kneading so that the content of the polar group is 0.01% by mass to 5% by mass, and the polar group is contained in the polymer block (B), wherein: When the polymer block (B) is present at the end of the hydrogenated block copolymer, the following steps are excluded: a polymerization initiator having a functional group reacts with the polymer block (B) at the end; and a modifier having a functional group reacts with the conjugated diene compound unit of the polymer block (B) as the active end. The modified hydrogenated block copolymer does not include the case where the polar group is bonded to the polymer block (A). <Condition (i)> The content of the vinyl aromatic compound unit in the block copolymer is 1% to 30% by mass; <Condition (ii)> The polymer block (B) comprises units (a) derived from 1,2-bonds and / or 3,4-bonds and units (b) derived from 1,4-bonds, and when the total content of the polymer block (B) is 100%, the content of the units (a) derived from 1,2-bonds and / or 3,4-bonds is 1% to 55%; <Condition (iii)> The polymer block (B) comprises an olefinic monomer unit (a1) obtained by hydrogenating the unit (a) derived from a 1,2-bond and / or 3,4-bond and an olefinic monomer unit (b1) obtained by hydrogenating the unit (b) derived from a 1,4-bond. When the total content of the polymer block (B) is 100%, the total content of the olefinic monomer unit (a1) and the olefinic monomer unit (b1) is 5% to 55%. <Condition (iv)> When the amount of the units (a) derived from 1,2-bonds and / or 3,4-bonds in the polymer block (B) is 100%, the amount of the ethylenic monomer units (a1) obtained by hydrogenating the units (a) is 80% or more.

22. The method for producing a modified hydrogenated block copolymer according to claim 21, wherein: After adding a stabilizer to the hydrogenated block copolymer, the modification step is performed.

23. The method for producing a modified hydrogenated block copolymer according to claim 21 or 22, wherein: In the modification step, the temperature of the hydrogenated block copolymer is set to 150°C to 260°C.

24. The method for producing a modified hydrogenated block copolymer according to claim 22, wherein: The stabilizer is selected from the group consisting of phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers.

25. The method for producing a modified hydrogenated block copolymer according to claim 23, wherein: In the modification step, the temperature of the hydrogenated block copolymer is set to 160°C to 250°C.

26. The method for producing a modified hydrogenated block copolymer according to claim 21 or 22, wherein: After the modification process, filtration was performed using a mesh.

27. A method for producing a resin composition, which is the method for producing a resin composition according to any one of claims 1 to 20, wherein: The component (I) is obtained by the method for producing a modified hydrogenated block copolymer according to any one of claims 21 to 26.

28. A molded product formed from the resin composition according to any one of claims 1 to 20.

29. The shaped article according to claim 28, which is a container.

30. The formed article according to claim 28, which is a cylindrical container.

31. The molded article according to claim 28, which is a housing.

32. The formed article according to claim 28, which is a sheet.

33. The molded article according to claim 28, which is a pipe.

34. A molded article, comprising a resin composition comprising: At least one resin selected from the group consisting of polyamide resins, acrylic resins, polyacetal resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, epoxy resins, and phenol resins; and A modified block copolymer having a polymer block (A) mainly composed of a vinyl aromatic compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit, in, The modified block copolymer is a modified block copolymer having a vinyl aromatic compound unit content of 1% to 30% by mass, a vinyl bond content of 1% to 55% in the polymer block (B) mainly composed of a conjugated diene compound unit, at least one selected from the group consisting of anhydride groups, carboxylic acid groups, and hydroxyl groups, and a polar group in the polymer block (B). When the polymer block (B) is present at a terminal of the modified block copolymer, the modified block copolymer does not include: a reaction product of a polymerization initiator having a functional group and the polymer block (B) at the terminal, and a case where the polar group is bonded to the conjugated diene compound unit of the polymer block (B) as the active terminal; and the modified block copolymer does not include a case where the polar group is bonded to the polymer block (A). The molded body satisfies the following conditions (I-1) to (II-1): <Condition (I-1)> For a strip test piece with a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the molded article, the tensile elongation at break at a tensile speed of 5 mm / min at -50°C is 15% or more; <Condition (II-1)> A strip test piece having a width of 10 mm, a length of 40 mm, and a thickness of 2 mm obtained from the molded article showed a peak at -60°C or lower in the viscoelasticity measurement under the conditions of a strain of 0.1% and a frequency of 1 Hz.

35. The molded article according to claim 34, wherein The hydrogenation rate of the conjugated diene compound unit in the modified block copolymer is 5% to 55%.

36. The molded article according to claim 34, wherein For a notched strip test piece having a width of 10 mm, a length of 80 mm, a thickness of 2 mm, and a notch shape obtained from the molded article according to claim 35, a Charpy impact test is conducted at -50°C with the impact direction being the side, in accordance with JIS K 7111-1, and the Charpy impact value is 10 kJ / m 2 above.

37. The molded article according to claim 35, wherein The hydrogenation rate of the conjugated diene compound unit in the modified block copolymer is 15% to 50%.

38. The molded article according to any one of claims 34 to 37, which is a container.

39. The molded article according to any one of claims 34 to 37, which is a cylindrical container.

40. The molded article according to any one of claims 34 to 37, which is a housing.

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