Adhesive and laminate

Abstract

To provide an adhesive exhibiting high adhesive strength to various materials, and a laminate using the adhesive.SOLUTION: An adhesive comprising a modified hydrogenated conjugated diene-based copolymer, wherein the modified hydrogenated conjugated diene-based copolymer has two or more polymer blocks selected from the group consisting of a polymer block (A) comprising a vinyl aromatic monomer unit as a main component, a polymer block (B) comprising a conjugated diene monomer unit as a main component, and a polymer block (C) having a vinyl aromatic monomer unit and a conjugated diene monomer unit, and in the modified hydrogenated conjugated diene-based copolymer, an unsaturated bond of a conjugated diene monomer unit is hydrogenated, A content of a vinyl aromatic monomer unit in the modified hydrogenated conjugated diene-based copolymer is 10% by mass or more and 80% by mass or less, and the modified hydrogenated conjugated diene-based copolymer has at least one polar group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive and a laminate. [Background technology]

[0002] BACKGROUND ART Laminates made of engineering plastics, which are excellent in strength and heat resistance, and metals, etc., have been proposed, and various adhesives have been proposed for bonding the layers together. For example, Patent Document 1 discloses a conjugated diene copolymer having a specific structure as a material for an adhesive between polypropylene and iron, and Patent Document 2 discloses a conjugated diene copolymer containing a polar group as a material for an adhesive between metal and polyolefin resin.

[0003] On the other hand, adhesives must be selected according to the material of each layer that is to be adhered, and there is a demand for adhesives that have high adhesive strength for a wide range of materials. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-155402 [Patent Document 2] International Publication No. 01 / 068785 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the adhesives disclosed in Patent Documents 1 and 2 still have the problem that there is room for improvement in terms of adhesive strength to various adherends.

[0006] Therefore, an object of the present invention is to provide an adhesive that exhibits high adhesive strength to various materials and a laminate using the adhesive. [Means for solving the problem]

[0007] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems of the conventional art, the present inventors have found that, in an adhesive containing a modified hydrogenated conjugated diene-based polymer having a specific structure, the above-mentioned problems of the conventional art can be solved by specifying the content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene-based polymer and specifying that the modified hydrogenated conjugated diene-based polymer has a polar group, and have thereby completed the present invention. That is, the present invention is as follows.

[0008] [1] An adhesive containing a modified hydrogenated conjugated diene copolymer, The modified hydrogenated conjugated diene copolymer is a polymer block (A) mainly composed of vinyl aromatic monomer units; a polymer block (B) mainly composed of conjugated diene monomer units; and, (C) a polymer block having a vinyl aromatic monomer unit and a conjugated diene monomer unit; The modified hydrogenated conjugated diene copolymer has unsaturated bonds of conjugated diene monomer units hydrogenated, the content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is 10% by mass or more and 80% by mass or less; The adhesive, wherein the modified hydrogenated conjugated diene copolymer has at least one polar group. [2] The polar group is at least one selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group; The adhesive described in [1] above. [3] the polar group is an amino group; The adhesive described in [1] above. [4] Layer (I), layer (II), and A laminate having an adhesive layer (III) provided between the layer (I) and the layer (II), The layer (I) and the layer (II) The material is mainly made of at least one material selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass; The layer (III) A layer made of the adhesive according to any one of [1] to [3] above. Laminate. [5] the layer (I) and the layer (II) are mainly made of different materials, The main material in the layer (I) and the layer (II) is The material is any one selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass; The laminate described in [4] above. [6] the layer (I) and the layer (II) are mainly made of different materials, The main material in the layer (I) and the layer (II) is The material is any one selected from the group consisting of polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polyolefin resins, SUS, and aluminum alloys; The laminate described in [4] above. [7] The main material in the layer (I) is At least one material selected from the group consisting of polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, SUS, and aluminum alloys; The main material in the layer (II) is It is a polyolefin resin. The laminate described in [4] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an adhesive that exhibits high adhesive strength to various materials, and a laminate using the adhesive. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. It should be noted that the following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be practiced with appropriate modifications within the scope of its gist.

[0011] 〔glue〕 The adhesive of the present embodiment contains a modified hydrogenated conjugated diene copolymer. The modified hydrogenated conjugated diene copolymer has two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units (hereinafter may be referred to as polymer block (A)), a polymer block (B) mainly composed of conjugated diene monomer units (hereinafter may be referred to as polymer block (B)), and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units (hereinafter may be referred to as polymer block (C)). In the modified hydrogenated conjugated diene copolymer, unsaturated bonds of the conjugated diene monomer units are hydrogenated, the content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is 10% by mass or more and 80% by mass or less, and the modified hydrogenated conjugated diene copolymer has at least one polar group. According to the above-mentioned configuration, high adhesive strength is exhibited to various materials.

[0012] (Modified hydrogenated conjugated diene polymer) The adhesive of the present embodiment contains a modified hydrogenated conjugated diene copolymer. The content of the modified hydrogenated conjugated diene copolymer in the adhesive of this embodiment is preferably 30% by mass or more, and may contain components other than the modified hydrogenated conjugated diene copolymer as long as the adhesive does not impair the appearance or adhesive strength. From the viewpoint of the adhesive strength and appearance described above, the content of the modified hydrogenated conjugated diene copolymer in the adhesive is more preferably 40% by mass or more, and even more preferably 50% by mass or more.

[0013] The modified hydrogenated conjugated diene copolymer has two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, in which the unsaturated bonds of the conjugated diene monomer units are hydrogenated and the copolymer has at least one polar group, and the amount of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is 10% by mass or more and 80% by mass or less.

[0014] The polymer block (A) mainly composed of vinyl aromatic monomer units has a vinyl aromatic monomer unit content of 80% by mass or more. Examples of vinyl aromatic compounds used to form vinyl aromatic monomer units 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. Among these, from the viewpoints of availability and productivity, styrene, α-methylstyrene, and 4-methylstyrene are preferred, and styrene is more preferred. The polymer block (A) may be constituted by one type of vinyl aromatic monomer unit, or may be constituted by two or more types of vinyl aromatic monomer units. From the viewpoint of the adhesive strength of the adhesive of this embodiment, the content of vinyl aromatic monomer units contained in the polymer block (A) is preferably more than 85 mass%, more preferably 90 mass%, even more preferably 95 mass%, and even more preferably 100 mass% (no other compounds are intentionally added).

[0015] The polymer block (B) mainly composed of conjugated diene monomer units has a conjugated diene monomer unit content of 80% by mass or more. The conjugated diene compound used to form the conjugated diene monomer unit is a diolefin having a pair of conjugated double bonds, including, but not limited to, 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, and farnesene. Among these, 1,3-butadiene and isoprene are preferable from the viewpoints of availability and productivity. The polymer block (B) may be composed of one type of conjugated diene monomer unit, or may be composed of two or more types of conjugated diene monomer units. From the viewpoint of adhesive strength of the adhesiveness of this embodiment, the content of the conjugated diene monomer unit contained in the polymer block (B) is preferably 85% by mass or more, more preferably 90% by mass, even more preferably 95% by mass, and even more preferably 100% by mass (no other compounds are intentionally added).

[0016] Furthermore, the modified hydrogenated conjugated diene copolymer may contain a polymer block (D) composed of a compound copolymerizable with the vinyl aromatic monomer unit and / or the conjugated diene monomer unit, other than the vinyl aromatic monomer unit and / or the conjugated diene monomer unit, within a range that does not impair the appearance of the laminate of the present embodiment described below and the adhesive strength of the adhesive of the present embodiment.

[0017] The vinyl aromatic compound and the conjugated diene compound used to form the vinyl aromatic monomer units and the conjugated diene monomer units contained in the polymer block (C) having the conjugated diene monomer units and the vinyl aromatic monomer units may be compounds that can be used in the polymer block (A) and the polymer block (B). The distribution of the vinyl aromatic monomer units in the polymer block (C) is not particularly limited, and the vinyl aromatic monomer units in the polymer block (C) may be uniformly distributed or tapered. In addition, there may be a plurality of regions where the vinyl aromatic monomer units are uniformly distributed and / or a plurality of regions where the vinyl aromatic monomer units are tapered, and there may be a plurality of segments with different contents of the vinyl aromatic monomer units. From the viewpoint of compatibility between the modified hydrogenated conjugated diene copolymer constituting the adhesive and other components, the polymer block (C) has a mass ratio of vinyl aromatic monomer units / conjugated diene monomer units of 79 / 21 to 21 / 79, preferably 75 / 25 to 25 / 75, and more preferably 70 / 30 to 30 / 70. This allows the polymer block (C) to be clearly distinguished from the polymer block (A) and the polymer block (B).

[0018] The modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment may contain monomer units formed from other compounds copolymerizable with the conjugated diene compound and the vinyl aromatic compound.

[0019] The structure of the modified hydrogenated conjugated diene copolymer used in the adhesive of the present embodiment is not particularly limited, but examples thereof include those having a structure represented by the following formula: (bc) n , c-(bc) n , b-(cb) n , (bc) m -X, (cb) m -X, [(bc) n ] m -X, [(cb) n ] m -X, [c-(bc)n ] m -X、[b-(c-b) n ] m -X、[(b-c) n -b] m -X、[(c-b) n -c] m -X、 (a-b) n 、b-(a-b) n 、a-(b-a) n 、(a-b) m -X、(b-a) m -X、[(a-b) n ] m -X、[(b-a) n ] m -X、[b-(a-b) n ] m -X、[a-(b-a) n ] m -X、[(a-b) n -a] m -X、[(b-a) n -b] m -X、 (a-c) n 、c-(a-c) n 、a-(c-a) n 、(a-c) m -X、(c-a) m -X、[(a-c) n ] m -X、[(c-a) n ] m -X、[c-(a-c) n ] m -X、[a-(c-a) n ] m -X、[(a-c) n -a] m -X、[(c-a) n -c] m -X、 c-(b-a) n 、c-(a-b) n 、 c-(a-b-a) n 、c-(b-a-b) n 、 a-c-(b-a) n 、a-c-(a-b) n 、 a-c-(b-a) n -b、[(a-b-c) n ] m -X、 [a-(b-c) n ] m -X、[(a-b) n -c] m -X、 [(a-b-a) n -c] m -X、 [(b-a-b) n -c] m -X、[(c-b-a) n ] m -X、 [c-(b-a) n ] m -X、[c-(a-b-a) n ] m -X、[c-(b-a-b) n ] m -X a-(b-c) n 、a-(c-b) n 、 a-(c-b-c) n 、a-(b-c-b) n 、 c-a-(b-c) n 、c-a-(c-b) n 、 c-a-(b-c) n -b、[(c-b-a) n ] m -X、 [c-(b-a) n ] m -X、[(c-b) n -a] m -X、 [(c-b-c) n -a] m -X、 [(b-c-b) n -a] m -X、[(a-b-c) n ] m -X、 [a-(b-c) n ] m -X、[a-(c-b-c) n ]m -X, [a-(bcb) n ] m -X b-(ac) n , b-(ca) n , b-(cac) n , b-(aca) n , cb-(ac) n , cb-(ca) n , cb-(ac) n -a, [(cab) n ] m -X, [c-(ab) n ] m -X, [(ca) n -b] m -X, [(cac) n -b] m -X, [(bcb) n -b] m -X, [(bac) n ] m -X, [b-(ac) n ] m -X, [b-(cac) n ] m -X, [b-(aca) n ] m -X In the above general formulas, a represents the polymer block (A), b represents the polymer block (B), and c represents the polymer block (C). n is an integer of 1 or more, and preferably an integer of 1 to 5. m is an integer of 2 or more, and preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a multifunctional initiator.

[0020] The adhesive of this embodiment preferably has high compatibility and / or affinity with polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polyolefin resins, polystyrene resins, metals, and glass, which tends to result in high adhesive strength in the laminate of this embodiment, which will be described later. To achieve the high compatibility and / or affinity, it is preferable that the solubility parameters (sp values) of the adhesive of this embodiment and the various resins described above are similar. Specifically, it is preferable that the solubility parameters of the modified hydrogenated conjugated diene copolymer described above are similar to those of the various resins described above. Polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, metals, and glass tend to have higher solubility parameters (sp values) than polyolefin resins. In order for the adhesive of this embodiment to exhibit high adhesion to various resin materials with different solubility parameters, it is necessary for the modified hydrogenated conjugated diene copolymer contained in the adhesive of this embodiment to have a polymer skeleton that is compatible with the various resins described above. Vinyl aromatic monomer units are known to have a higher sp value than conjugated diene monomer units. Therefore, by including two or more polymer blocks selected from the group consisting of polymer block (A) primarily composed of vinyl aromatic monomer units, polymer block (B) primarily composed of conjugated diene monomer units, and polymer block (C) containing vinyl aromatic monomer units and conjugated diene monomer units, the polymer block (A) and / or polymer block (C) containing vinyl aromatic monomer units exhibit compatibility and / or affinity with polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, metals, and glass, which have high sp values, and the polymer block (B) and / or polymer block (C) containing conjugated diene monomer units exhibit compatibility and / or affinity with polyolefin resins, thereby achieving high adhesiveness. From the viewpoint of improving adhesion to at least one material selected from the group consisting of polyolefin resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, SUS, and aluminum alloys, the modified hydrogenated conjugated diene copolymer preferably has the polymer block (A) and the polymer block (B).

[0021] The modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment has at least one polar group, which tends to improve compatibility and / or affinity with polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, metals, and glass. Examples of the polar group include, but are not limited to, atomic groups containing at least one functional group selected from a hydroxyl group, a carboxyl group, a dicarboxyl 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 thioaldehyde group, a carboxylic acid ester group, an amide group, a sulfonic acid group, a sulfonate ester group, a phosphoric acid group, a phosphoric acid ester group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an oxetanyl group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxy silicon group, a tin halide group, a boronic acid group, a boron-containing group, a boronate salt group, an alkoxytin group, and a phenyltin group. In terms of the adhesiveness of the adhesive of this embodiment, acid anhydride groups, amino groups, dicarboxyl groups, carboxyl groups, epoxy groups, and oxetanyl groups are preferred, and amino groups are more preferred.

[0022] Furthermore, the modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment has hydrogenated unsaturated bonds derived from the conjugated diene compound. Hydrogenation of the conjugated diene monomer units, which have excellent compatibility with polyolefin resins, reduces the difference in sp value between the polymer blocks (B) and (C) of the modified hydrogenated conjugated diene copolymer and the polyolefin resin, improving the compatibility between the modified hydrogenated conjugated diene copolymer and the polyolefin resin, and tending to improve adhesion to the polyolefin resin. Furthermore, promotion of microphase separation between the polymer block (A) and / or the polymer block (C) and the polymer block (B) improves the compatibility and / or affinity of the polymer block (A) and / or the polymer block (C) with polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, metals, and glass, and tends to improve adhesion. From the above viewpoint, the hydrogenation rate (hydrogenation rate) of the modified hydrogenated conjugated diene copolymer used in the adhesive of the present embodiment is preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, and still more preferably 70% or more.

[0023] The content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment is 10% by mass or more and 80% by mass or less. When the content of vinyl aromatic monomer units is 80% by mass or less, the modified hydrogenated conjugated diene copolymer tends to have sufficient flexibility. When the modified hydrogenated conjugated diene copolymer has sufficient flexibility, in the laminate of this embodiment described below, the wettability between the adhesive layer (III) made of the adhesive of this embodiment and the layers (I) and (II) made of a predetermined resin material that are in contact with the adhesive layer (III) is improved, and sufficient adhesion tends to be obtained. When the content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is 10% by mass or more, the sp value is prevented from becoming too low, and sufficient adhesion to polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, metals, and glass tends to be obtained. The content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is preferably 15% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 80% by mass or less, even more preferably 25% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 80% by mass or less. The content of the vinyl aromatic monomer unit in the modified hydrogenated conjugated diene copolymer can be measured by the method described in the Examples below, and can be controlled to fall within the above-mentioned numerical range by adjusting the amount of vinyl aromatic compound added in the polymerization step and the polymerization time.

[0024] The modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene monomer units and units (b) derived from 1,4-bonds. When the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds (hereinafter sometimes referred to as the vinyl bond content) is preferably 10% or more. A vinyl bond content of 10% or more tends to improve moldability. From the above viewpoint, the vinyl bond content is preferably 20% or more, more preferably 25% or more, and even more preferably 35% or more. The vinyl bond amount can be measured by the method described in the Examples below, and as described below, it can be controlled to fall within the above-mentioned range by using a vinyl bond amount regulator (vinylating agent).

[0025] Furthermore, the weight average molecular weight (Mw) (hereinafter also referred to as "Mw") of the modified hydrogenated conjugated diene copolymer used in the adhesive of the present embodiment is preferably 35,000 to 600,000, more preferably 40,000 to 400,000, and even more preferably 45,000 to 300,000, from the viewpoint of the formability of the laminate of the present embodiment described below. The weight-average molecular weight (Mw) of the modified hydrogenated conjugated diene copolymer is the weight-average molecular weight (Mw) calculated based on the molecular weight of the peak in the chromatogram obtained by measurement by gel permeation chromatography (GPC) and a calibration curve (prepared using the peak molecular weight of the standard polystyrene) obtained from the measurement of commercially available standard polystyrene. The molecular weight distribution of the hydrogenated conjugated diene block copolymer before modification can also be determined by GPC measurement, similar to that of the modified conjugated diene copolymer. The molecular weight distribution is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The single-peak molecular weight distribution of the modified hydrogenated conjugated diene copolymer measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less. The weight average molecular weight and molecular weight distribution of the modified hydrogenated conjugated diene block copolymer can be controlled within the above numerical range by adjusting the polymerization conditions such as the amount of monomer added, timing of addition, polymerization temperature, and polymerization time.

[0026] (Method for producing modified hydrogenated conjugated diene copolymer) The modified hydrogenated conjugated diene copolymer used in the adhesive of the present embodiment can be produced, but is not limited to, by, for example, polymerizing a conjugated diene compound and a vinyl aromatic compound in an organic solvent using an organic alkali metal compound as a polymerization initiator to obtain a conjugated diene copolymer, followed by a hydrogenation reaction and a modification reaction. The hydrogenation reaction and the modification reaction are not limited to this order, and may be performed in the reverse order.

[0027] <Polymerization process> The polymerization may be carried out by batch polymerization, continuous polymerization, or a combination thereof. The polymerization temperature is generally 0 to 180°C, preferably 20 to 160°C, and more preferably 30 to 150°C. The polymerization time varies depending on the target conjugated diene copolymer, but is usually within 48 hours, preferably 0.1 to 10 hours, and more preferably 0.5 to 5 hours from the viewpoint of obtaining a conjugated diene copolymer having a narrow molecular weight distribution and high strength. The atmosphere of the polymerization system is not particularly limited as long as it is in a pressure range sufficient to maintain the nitrogen and organic solvent in a liquid phase. It is preferable that impurities that may inactivate the polymerization initiator and the living polymer, such as water, oxygen, carbon dioxide gas, etc., are not present in the polymerization system.

[0028] Examples of organic solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

[0029] As the organic alkali metal compound serving as the polymerization initiator, an organic lithium compound is preferred. The organolithium compound includes an organomonolithium compound, an organodilithium compound, and an organopolylithium compound. Examples of the organolithium compound include, but are not limited to, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and lithium piperidide. When an organolithium compound containing N, such as lithium piperidide, is used as a polymerization initiator, an amino group-modified conjugated diene copolymer having an atomic group where X=0 in NHx is obtained. These polymerization initiators may be used alone or in combination of two or more. Among these, n-butyllithium, sec-butyllithium, and lithium piperidide are preferred as the polymerization initiator from the viewpoint of polymerization activity. The amount of the organic alkali metal compound used as the polymerization initiator depends on the molecular weight of the target conjugated diene copolymer, but is generally preferably in the range of 0.01 to 1.5 phm (parts by mass per 100 parts by mass of monomer), more preferably in the range of 0.02 to 0.3 phm, and even more preferably in the range of 0.05 to 0.2 phm.

[0030] The vinyl bond content of the modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment can be controlled by using a Lewis base, such as an ether or an amine compound, as a vinyl bond content adjuster (hereinafter referred to as a vinylizing agent). The amount of vinylating agent used can be adjusted depending on the desired amount of vinyl bonds. The vinylating agent is not limited to the following, but examples thereof include ether compounds and tertiary amine compounds. Examples of the ether compound include a linear ether compound and a cyclic ether compound. Examples of linear ether compounds include, but are not limited to, dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Furthermore, examples of cyclic ether compounds include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol. 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-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N",N"-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis[2-(N,N-dimethylamino)ethyl]ether. These may be used alone or in combination of two or more. The tertiary amine compound is preferably a compound having two amines, and among them, a compound having an intramolecularly symmetric structure is more preferred, and N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, and 1,2-dipiperidinoethane are even more preferred.

[0031] In the process for producing the modified hydrogenated conjugated diene copolymer, polymerization can be carried out using a conjugated diene compound and a vinyl aromatic compound in the coexistence of the above-mentioned vinylating agent, an organolithium compound as a polymerization initiator, and an alkali metal alkoxide. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M is an alkali metal and R is an alkyl group). By using an alkali metal alkoxide in the polymerization step, the vinyl bond amount, molecular weight distribution, polymerization rate, block ratio, etc. can be controlled.

[0032] The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoints of a high vinyl bond content, a narrow molecular weight distribution, a high polymerization rate, and a high block ratio. Examples of alkali metal alkoxides include, but are not limited to, sodium alkoxides, lithium alkoxides, and potassium alkoxides having an alkyl group with 2 to 12 carbon atoms, preferably sodium alkoxides and potassium alkoxides having an alkyl group with 3 to 6 carbon atoms, and more preferably sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide. Among these, sodium alkoxides such as sodium t-butoxide and sodium t-pentoxide are more preferred.

[0033] <Hydrogenation reaction step> The method for hydrogenating the unsaturated bonds derived from the conjugated diene monomer units of the conjugated diene copolymer is not particularly limited. For example, hydrogen can be supplied to the conjugated diene copolymer obtained in the polymerization step in the presence of a hydrogenation catalyst to perform hydrogenation, thereby obtaining a hydrogenated conjugated diene copolymer in which the double bond residues of the conjugated diene monomer units are hydrogenated. The hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst used during hydrogenation, and the hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst, hydrogen feed rate, pressure, temperature, etc. during hydrogenation. The hydrogenation reaction step is preferably carried out after the reaction for producing the conjugated diene copolymer before hydrogenation has stopped.

[0034] <Denaturation process> The modified hydrogenated conjugated diene copolymer used in the adhesive of this embodiment has a polar group, and it is preferable that the polar group is at least one type of polar group selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group. The method for introducing the polar group is not particularly limited, and examples thereof include a method for introducing the polar group using a polymerization initiator having a predetermined functional group that becomes the polar group, a method for polymerizing an unsaturated monomer having the functional group, and a method for performing an addition reaction of a modifier that forms or contains a functional group at a living terminal.

[0035] Examples of the "modifier" include, but are not limited to, aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid; and other compounds. Other examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and ε-caprolactam.

[0036] Another method for introducing a polar group into a conjugated diene copolymer includes, for example, reacting a conjugated diene copolymer with an organic alkali metal compound such as an organolithium compound (metallation reaction), and then adding a modifier having a functional group to the polymer to which the organic alkali metal compound has been added.

[0037] Another method for introducing polar groups is, for example, a production method in which an atomic group having a functional group is directly graft-added to an unmodified conjugated diene copolymer. Examples of the grafting method include a method of reacting a radical initiator, a conjugated diene copolymer, and the modifier in a solution containing them; a method of reacting a radical initiator, a conjugated diene copolymer, and the modifier under heating and melting; and a method of reacting a conjugated diene copolymer without a radical initiator and a compound containing the modifier under heating and melting. Examples of the reaction method include a method of melt-kneading the components using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, etc. From the viewpoints of cost and production stability, a method using a single-screw, twin-screw, or multi-screw extruder is preferred, and a method using a twin-screw extruder is more preferred. During the reaction step, the raw materials may be dry blended and added all at once, or each raw material may be fed separately, or the same raw material may be added stepwise. The screw rotation speed is preferably 50 to 400 rpm, more preferably 100 to 350 rpm, from the viewpoint of uniformly adding the modifier, and is preferably 150 to 300 rpm, from the viewpoint of preventing deterioration of the resin due to shear and uniformly adding the modifier. The kneading temperature is preferably 100°C to 350°C from the viewpoint of melting the conjugated diene copolymer and generating radicals from the radical initiator, more preferably 120°C to 300°C, and even more preferably 150°C to 250°C from the viewpoint of controlling the addition amount and suppressing deterioration of the resin due to heat. In order to prevent deactivation of radical active species by oxygen, it is preferable to carry out the melt-kneading under an inert gas such as nitrogen.

[0038] The radical initiator is not limited to, but includes, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and peroxydicarbonate. Preferably, it has a one-minute half-life temperature in the kneading temperature range, more preferably, a one-minute half-life temperature of 150°C to 250°C. Examples of such radical initiators include, but are not limited to, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric acid, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, and 2,5-dimethyl-2,5-di(benzoylperoxy)hexane. Examples of peroxides include hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. In particular, from the viewpoint of compatibility with conjugated diene copolymers, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are preferred, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne are more preferred.

[0039] Another method for introducing polar groups into a conjugated diene copolymer includes secondary modification, in which a functional group of the primarily modified conjugated diene copolymer obtained by the above-mentioned method is reacted with an atomic group having a predetermined functional group. Combinations of polar groups include, but are not limited to, for example, an amino group and a dicarboxyl group, an acid anhydride group and an amino group, a hydroxyl group; an isocyanate group and a hydroxyl group, a carboxyl group and an amino group, an acid anhydride group and a hydroxyl group, a silanol group and a hydroxyl group, and an epoxy group and a carboxyl group. From the viewpoint of reactivity, however, combinations of an amino group and a dicarboxyl group, an acid anhydride group and an amino group, a silanol group and a hydroxyl group, a dicarboxyl group and an amino group, and an epoxy group and a carboxyl group are preferred, and combinations of an amino group and a dicarboxyl group, and an acid anhydride group and an amino group are more preferred.

[0040] As the primary modification, the methods for bonding an epoxy group, an acid anhydride group, or a hydroxyl group to a conjugated diene copolymer include the methods described above, and the primary modifying agent includes the above-mentioned modifying agent, an epoxy group-containing polymerizable compound, and the like.

[0041] As the primary modification, methods for bonding silanol groups to a conjugated diene copolymer include the methods described above. Examples of primary modifiers for bonding silanol groups include, but are not limited to, bis-(3-triethoxysilylpropyl)-tetrasulfane, bis-(3-triethoxysilylpropyl)-disulfane, ethoxysiloxane oligomers, epoxy group-containing polymerizable compounds, and hydrolysates of compounds having alkoxysilane groups listed above as epoxy group-containing polymerizable compounds.

[0042] As the primary modification, methods for bonding amino groups to a conjugated diene copolymer include the methods described above. Primary modifying agents for bonding amino groups include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone, and 1-methyl-3-(2-ethoxyethyl)-2-imidazolidinone. , 1,3-di-(2-ethoxyethyl)-2-imidazolidinone, 1,3-dimethylethylenethiourea, N,N'-diethylpropyleneurea, N-methyl-N'-ethylpropyleneurea, 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2-piperidone, 1-isopropyl-5,5-dimethyl-2-piperidone, and the like.

[0043] Examples of a method for bonding a secondary modifier to a primarily modified conjugated diene polymer having an amino group bonded thereto include the methods described above. Examples of the secondary modifier include, but are not limited to, aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid. Other examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, and 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

[0044] The shape of the modified hydrogenated conjugated diene copolymer used in the adhesive of the present embodiment is not particularly limited, and examples thereof include pellets, sheets, strands, chips, etc. After melt-kneading, the copolymer can also be directly molded into a molded product.

[0045] (Other components that make up the adhesive) The adhesive of the present embodiment contains the above-described modified hydrogenated conjugated diene copolymer, and may also contain various additives within limits that do not impair the effects of the adhesive. Examples of the additives include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antioxidants, nucleating agents, plasticizers, impact modifiers, compatibilizers, antifoaming agents, thickeners, crosslinking agents, surfactants, lubricants, mold release agents, antiblocking agents, processing aids, antistatic agents, flame retardants, flame retardant assistants, fillers, and colorants. These additives may be used alone or in any combination of two or more in any ratio. Examples of the heat stabilizer and antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides. Flame retardants are broadly classified into halogen-based and non-halogen-based flame retardants, with non-halogen-based flame retardants being environmentally preferable. Non-halogen-based flame retardants include phosphorus-based flame retardants, hydrated metal compound (aluminum hydroxide, magnesium hydroxide) flame retardants, nitrogen-containing compound (melamine-based, guanidine-based) flame retardants, and inorganic compound (borate, molybdenum compound) flame retardants. Fillers are broadly classified into organic fillers and inorganic fillers. Examples of organic fillers include naturally occurring polymers such as starch, cellulose fine particles, wood flour, soybean pulp, rice husks, and bran, as well as modified products thereof. Examples of inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloons, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, and carbon fibers.

[0046] (Adhesive manufacturing method) The adhesive of this embodiment can be produced by mixing the above-mentioned modified hydrogenated conjugated diene copolymer with the above-mentioned additives as required. The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, by mixing the above-mentioned raw material components simultaneously or in any order, a composition in which the components are uniformly dispersed, i.e., a composition that constitutes an adhesive, can be obtained. For more uniform mixing and dispersion, it is preferable to melt-mix predetermined amounts of the raw material components. For example, the raw material components of the composition may be mixed in any order and then heated, or all of the raw material components may be mixed while being melted sequentially. Alternatively, all of the material components may be mixed while being dissolved in an organic solvent or the like. The production conditions for producing the composition by these methods are not limited, and can be appropriately set according to well-known conditions. The temperature during melt mixing may be any temperature at which at least one of the raw material components is in a molten state, but a temperature at which all the components used are melted is usually selected, and the melting and mixing can generally be carried out at 150 to 250°C.

[0047] [Laminate] The laminate of this embodiment has a layer (I), a layer (II), and an adhesive layer (III) provided between the layer (I) and the layer (II), wherein the layer (I) and the layer (II) are mainly made of at least one material selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass, and the layer (III) is a layer made of the adhesive of this embodiment described above.

[0048] (layer (I), layer (II)) As described above, the laminate of this embodiment has a layer (I), a layer (II), and an adhesive layer (III) provided between the layer (I) and the layer (II), and the layer (I) and the layer (II) are mainly made of at least one material selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass. Layer (I) and layer (II) are mainly made of at least one selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass, thereby providing a laminate with excellent heat resistance and strength. Here, in the laminate of this embodiment, with regard to the materials constituting Layer (I) and Layer (II), the term "mainly composed of" means that, based on 100% by mass of the total materials constituting Layer (I) and Layer (II), at least one selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass accounts for 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.

[0049] In recent years, due to increasing demands for physical properties, laminates of different materials are in demand. Therefore, the layer (I) and the layer (II) are each made mainly of a different material, and the main material of the layer (I) and the layer (II) is preferably any one selected from the group consisting of polyamide resin, polycarbonate resin, polyethylene terephthalate resin, ABS resin, polyvinyl chloride resin, polystyrene resin, polyolefin resin, metal, and glass, and more preferably any one selected from the group consisting of polycarbonate resin, polyethylene terephthalate resin, ABS resin, polyvinyl chloride resin, polyolefin resin, SUS, and aluminum alloy.

[0050] Furthermore, from the viewpoints of low cost and moldability, a laminate based on a polyolefin resin is desired. From these viewpoints, it is preferred that the layer (I) is mainly made of at least one selected from the group consisting of a polycarbonate resin, a polyethylene terephthalate resin, an ABS resin, a polyvinyl chloride resin, SUS, and an aluminum alloy, and the layer (II) is mainly made of a polyolefin resin.

[0051] The polyamide resin may be any resin that falls within the category of polyamide resins, and is not limited to the following, but examples thereof include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene Polysebacamide (Nylon 610), polyhexamethylene dodecamide (Nylon 612), polydecamethylene adipamide (Nylon 106), polydecamethylene sebacamide (Nylon 1010), polydecamethylene dodecamide (Nylon 1012), polyundecane amide (Nylon 11), polydodecanamide (Nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (Nylon 6 / 66) ( / indicates copolymer).(hereinafter the same), polycaproamide / 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 / polycaproamide copolymer (nylon 66 / 6I / 6), Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Nylon 6T / 6I), Polyhexamethylene terephthalamide / Polyundecane amide copolymer (Nylon 6T / 11), Polyhexamethylene terephthalamide / Polydodecanamide copolymer (Nylon 6T / 12), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Nylon 66 / 6T / 6I) ), Polyxylylene adipamide (Nylon XD6), Polyxylylene sebacamide (Nylon XD10), Polyhexamethylene terephthalamide / Polypentamethylene terephthalamide copolymer (Nylon 6T / 5T), Polyhexamethylene terephthalamide / Poly-2-methylpentamethylene terephthalamide copolymer (Nylon 6T / M5T), Polypentamethylene terephthalamide / Polydecamethylene terephthalamide copolymer (Nylon 5T / 10T) ), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polydecamethylene terephthalamide / polyhexamethylene dodecane amide copolymer (nylon 10T / 612), polydecamethylene terephthalamide / polyhexamethylene adipamide copolymer (nylon 10T / 66), polydodecamethylene terephthalamide (nylon 12T), and other polyamide resins (including copolymers thereof).

[0052] The polycarbonate resin may be any resin in which the bonding portions between monomer units are composed of carbonate groups (-O-(C=O)-O-) and which falls into the category of polycarbonate resins. Polycarbonate resins can be classified into aromatic polycarbonate resins and aliphatic polycarbonate resins, which are aliphatic carbons, and either can be used.

[0053] Examples of monomers constituting the aromatic polycarbonate resin include, but are not limited to, dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl; 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene; dihydroxynaphthalenes such as naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene;2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl- 4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis( bis(hydroxyaryl)alkanes such as 1,1-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane;1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-t-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-t-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)- bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane and 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; and the like.

[0054] Among the monomers serving as raw materials for polycarbonate resins, carbonate precursors include, but are not limited to, carbonyl halides, carbonate esters, etc. One type of carbonate precursor may be used, or two or more types may be used in any combination and ratio. Examples of carbonyl halides include, but are not limited to, phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds; and the like. Examples of carbonate esters include, but are not limited to, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0055] The aliphatic polycarbonate is not particularly limited as long as the main chain contains only aliphatic groups, and examples thereof include, but are not limited to, aliphatic polycarbonates obtained by copolymerization of a cyclic ether and carbon dioxide, aliphatic polycarbonates obtained by polycondensation of an aliphatic diol with carbon dioxide, phosgene, a carbonate diester, or the like, aliphatic polycarbonates obtained by ring-opening polymerization of a cyclic carbonate, and aliphatic polycarbonates obtained by polycondensation of an aliphatic dihalide with a carbonate.

[0056] The polyethylene terephthalate resin may be any resin that falls within the category known as a polyethylene terephthalate resin, and is not limited to the following. However, a polymer obtained by a polymerization reaction between a diol component containing at least 50 mol % or more of ethylene glycol and a carboxylic acid component containing at least 50 mol % or more of terephthalic acid is more preferred. Examples of carboxylic acids include, but are not limited to, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid, and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid and derivatives thereof. Furthermore, examples of diol components other than ethylene glycol include, but are not limited to, aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol; alicyclic diols such as 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralindimethanol, norbornanedimethanol, tricyclodecanedimethanol, and pentacyclododecanedimethanol; and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S. Examples of the polymer include, but are not limited to, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate), and polyethylene (terephthalate / decanedicarboxylate).

[0057] Any ABS resin containing the three components acrylonitrile, butadiene, and styrene can be used, including commercially available ABS resins. Examples of ABS resins include, but are not limited to, types in which acrylonitrile and styrene are grafted onto butadiene latex; blends of acrylonitrile and styrene copolymers with nitrile rubber (NBR), a copolymer of acrylonitrile and butadiene; copolymers obtained by block or graft polymerization of one or more monomers, such as aromatic vinyl monomers and vinyl cyanide monomers, onto diene rubber; and blends of such copolymers. Examples of diene rubbers include polybutadiene, polyisoprene, acrylonitrile-butadiene copolymers, and styrene-butadiene copolymers. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, and various alkyl-substituted styrenes. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and various halogen-substituted acrylonitriles. Specific examples of the above-mentioned copolymers and blends thereof include acrylonitrile-butadiene-styrene terpolymers and acrylonitrile-styrene binary copolymers polymer alloyed with polybutadiene. There are no particular limitations on the composition ratio of the three monomers that make up the ABS resin.

[0058] The polyvinyl chloride resin may be any resin that falls within the category of polyvinyl chloride resins, and includes, but is not limited to, a homopolymer of vinyl chloride and a copolymer of vinyl chloride with another monomer copolymerizable with vinyl chloride. Examples of the copolymerizable monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and styrene; alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and methyl (meth)acrylate; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; and vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more.

[0059] The polystyrene resin may be any resin that falls within the category of polystyrene resins, and is not limited to the following, and examples thereof include styrene homopolymers and copolymers of styrene and other monomers, which may be used alone or in combination of two or more.Specific examples of styrene homopolymers include general-purpose polystyrene (GPPS) having an atactic structure and syndiotactic polystyrene having a syndiotactic structure.

[0060] The polyolefin resin may be any resin that falls into the category of polyolefin resins, and includes, but is not limited to, polyethylene resin and polypropylene resin. Examples of polyethylene resins include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers of ethylene and an α-olefin having 3 to 8 carbon atoms. When the polyethylene resin is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, examples of the α-olefin in the copolymer include propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Examples of polypropylene resins include propylene homopolymers synthesized using Ziegler-Natta catalysts and random or block copolymers of propylene and α-olefins. In the case of copolymers of propylene and α-olefins, the proportion of α-olefins is preferably 30% by mass or less, more preferably 35% by mass or less, based on 100% by mass of polypropylene resin. Specific examples of polypropylene resins include copolymers of propylene and α-olefins having 2 to 8 carbon atoms. When the polypropylene resin is a copolymer of propylene and α-olefins having 2 to 8 carbon atoms, examples of the α-olefins in the copolymer include ethylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. These polyolefin resins can be synthesized by conventionally known methods. The polyolefin resin may be subjected to a surface treatment such as a corona treatment from the viewpoint of improving adhesiveness, but is preferably untreated from the viewpoint of cost and / or environmental pollution.

[0061] The glass may be any material that falls within the category known as glass, and can be appropriately selected depending on the physical properties required for the laminate of this embodiment.

[0062] The metal may be any metal as long as it belongs to the category called metal and can be appropriately selected depending on the physical properties required for the laminate of this embodiment. Examples of metals include, but are not limited to, SUS, aluminum alloy, etc.

[0063] [Method for manufacturing laminate] As described above, the laminate of this embodiment is a laminate having an adhesive layer (III) provided between the layer (I) and the layer (II), and can be produced by widely employing known methods. Examples of such methods include a co-extrusion method in which the individual molten resins forming Layers (I) to (III) are melted in an extruder and fed into a multi-layer die, where they are laminated and molded to form an inflation film, T-die film, sheet, pipe, or the like; a co-injection molding method in which the individual molten resins are injected into the same mold with a time lag; and a method in which the adhesive component is dissolved in an organic solvent or the like and applied to the adherend. Alternatively, extrusion lamination molding can be employed in which a resin film constituting any one of the layers is formed in advance, and the other layers are melt-extruded onto the resin film. Furthermore, the laminate of this embodiment can also be produced by molding resin films constituting each layer in advance and fusing these layers by applying heat. When the layer (I) and / or the layer (II) is made of metal, the laminate can be produced by a method of dissolving the adhesive component in an organic solvent or the like and applying it to the adherend, or by a method of applying the adhesive component in a molten state to the upper surface of the metal, or the like.

[0064] After a laminate is obtained by the above-mentioned molding method, it can be stretched to form a stretched laminate. The stretched laminate may be heat-set or may be used as a product without heat-setting. If heat-setting is not performed, the stretched laminate can be used as a shrink film because it has the property of shrinking when the stress is released by heating the stretched laminate afterwards. Furthermore, these can be subjected to secondary processing such as vacuum forming and pressure forming to form draw-formed containers, etc.

[0065] Furthermore, in the laminate of this embodiment, an adhesive layer (layer (III)) may be provided in advance on both adherends (layer (I) and layer (II)), and then the adherends may be laminated and bonded. To achieve strong bonding, the laminate may be pressurized, and pressure may be applied to the entire laminate or only to the portions where the adhesive layers are provided. There are no particular limitations on the method of pressurization, and there are also no particular limitations on the pressure, as long as it is a pressure that does not significantly deform the adhesive layers.

[0066] The shape of the laminate of this embodiment is not limited, and may be any shape, such as a flat shape such as a film, sheet, or plate, or a pipe, bag, or irregular shape.

[0067] The laminate of the present embodiment may have a predetermined layer (hereinafter, sometimes referred to as "other layer") other than the layer (I), the layer (II), and the adhesive layer (III).

[0068] Furthermore, various additives and the like can be blended into each layer of the laminate of this embodiment, as long as the effects of the present invention are not impaired. Examples of additives include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antioxidants, nucleating agents, plasticizers, impact modifiers, compatibilizers, antifoaming agents, thickeners, crosslinking agents, surfactants, lubricants, mold release agents, antiblocking agents, processing aids, antistatic agents, flame retardants, flame retardant assistants, fillers, colorants, etc. These additives may be used alone or in any combination and ratio of two or more. Examples of the heat stabilizer and antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides. Flame retardants are broadly classified into halogen-based and non-halogen-based flame retardants, with non-halogen-based flame retardants being preferred from an environmental perspective. Examples of non-halogen-based flame retardants include phosphorus-based flame retardants, hydrated metal compound (aluminum hydroxide, magnesium hydroxide) flame retardants, nitrogen-containing compound (melamine-based, guanidine-based) flame retardants, and inorganic compound (borate, molybdenum compound) flame retardants. Fillers are broadly classified into organic fillers and inorganic fillers. Examples of organic fillers include naturally occurring polymers such as starch, cellulose fine particles, wood flour, soybean pulp, rice husks, and bran, as well as modified products thereof. Examples of inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloons, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, and carbon fibers. [Example]

[0069] Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples in any way.

[0070] The structures of the hydrogenated conjugated diene copolymers used in the adhesives of the following Examples and Comparative Examples, as well as methods for measuring the physical properties and methods for evaluating the laminates, are shown below.

[0071] [Evaluation of Structure, Properties, and Laminates of Hydrogenated Conjugated Diene Copolymers] The structure of the hydrogenated conjugated diene polymer and the methods for measuring its physical properties are shown below.

[0072] ((1) Vinyl bond content of hydrogenated conjugated diene copolymer) The vinyl bond content relative to the total 100 mol% of the conjugated diene monomer units of the hydrogenated conjugated diene copolymer was determined by proton nuclear magnetic resonance ( 1 H-NMR). The measurement was performed using an ECS400 (manufactured by JEOL), deuterated chloroform as the solvent, a sample concentration of 50 mg / mL, an observation frequency of 400 MHz, tetramethylsilane as the chemical shift standard, a pulse delay of 2.904 seconds, 64 scans, a pulse width of 45°, and a measurement temperature of 26°C. The amount of vinyl bonds was calculated from the ratio of 1,4-bonds to 1,2-bonds after calculating the integral value per 1H of each bond type from the integral values ​​of the signals assigned to 1,4-bonds and 1,2-bonds.

[0073] ((2) Hydrogenation rate of unsaturated bonds in conjugated diene monomer units of hydrogenated conjugated diene copolymers) The hydrogenation rate of hydrogenated conjugated diene copolymers was measured by proton nuclear magnetic resonance ( 1 H-NMR). The measurement conditions and the method of processing the measurement data were the same as those in (1) above. The hydrogenation rate was calculated by calculating the integral values ​​of the signals derived from the remaining double bonds at 4.5 to 5.5 ppm and the signals derived from the hydrogenated conjugated dienes, and then calculating the ratio thereof.

[0074] ((3) Content of vinyl aromatic monomer units in hydrogenated conjugated diene copolymer (hereinafter also referred to as "styrene content")) The content of vinyl aromatic monomer units was measured by proton nuclear magnetic resonance ( 1 H-NMR was used for the measurement. The measurement equipment was ECS400 (manufactured by JEOL), the solvent was deuterated chloroform, the sample concentration was 50 mg / mL, the observation frequency was 400 MHz, tetramethylsilane was used as the chemical shift standard, the pulse delay was 2.904 seconds, the number of scans was 64, the pulse width was 45°, and the measurement temperature was 26°C. The styrene content was calculated using the integrated value of the total styrene aromatic signal from 6.2 to 7.5 ppm in the spectrum. The styrene content was also confirmed by calculating the content of vinyl aromatic monomer units for each polymer sampled at each step in the polymerization process of the conjugated diene copolymer before hydrogenation.

[0075] ((4) Weight-average molecular weight of hydrogenated conjugated diene copolymer) The weight average molecular weight of the hydrogenated conjugated diene copolymer was measured by GPC [apparatus: HLC8220 (manufactured by Tosoh Corporation), column: TSKgelSUPER-HZM-N (4.6 mm×30 cm)]. Tetrahydrofuran was used as the solvent. The weight average molecular weight was determined from the molecular weight of the peak in the chromatogram using a calibration curve (prepared using the peak molecular weight of the standard polystyrene) obtained from the measurement of commercially available standard polystyrene. When there are multiple peaks in the chromatogram, the weight average molecular weight is calculated from the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram).

[0076] ((5) Modification Ratio of Amino Group-Modified Hydrogenated Conjugated Diene Copolymer) The adsorption property of modified components was utilized in a GPC column packed with silica gel. For a sample solution containing a hydrogenated conjugated diene copolymer and a low-molecular-weight internal standard polystyrene (PS), the ratio of the hydrogenated conjugated diene copolymer to the standard polystyrene in the chromatogram measured in (4) above was compared with the ratio of the hydrogenated conjugated diene block copolymer to the standard polystyrene in the chromatogram measured using a silica column GPC [apparatus: LC-10 (Shimadzu Corporation), column: Zorbax (DuPont)], and the amount of adsorption to the silica column was calculated from the difference, and this ratio was taken as the modification rate. The modification rate was calculated as the ratio (%) of terminal amino groups with a specific structure using the following formula.

[0077]

number

[0078] a: Area (%) of the total polymer measured in polystyrene gel (PLgel) b: Area (%) of low molecular weight internal standard PS measured on polystyrene gel (PLgel). c: Area (%) of total polymer measured on a silica-based column (Zorbax) d: Area (%) of low molecular weight internal standard PS measured on a silica-based column (Zorbax)

[0079] ((6) Modification Ratio of Maleic Anhydride-Modified Hydrogenated Conjugated Diene Copolymer) The maleic anhydride-modified hydrogenated conjugated diene copolymer was dissolved in toluene and titrated with a methanol solution of sodium methoxide with a factor of 1±0.05 to calculate the coefficient of reactivity.

[0080] The properties of the laminate were evaluated as follows.

[0081] ((7) Adhesiveness (adhesive strength)) In the examples and comparative examples, a laminate was obtained by overlapping the material (thickness: 2 mm) constituting the layer (I) and / or layer (II) described below with the adhesive layer (thickness: 2 mm; layer (III)) described below, applying residual heat for 4 minutes, and then pressing them together with a heat press for 4 minutes. A 1 cm wide cut was made in the adhesive layer (layer (III)) of the laminate obtained as described above, and a peel test was performed using a tensile tester over a length of 10 cm or more, and the adhesive strength (N / cm) was calculated from the obtained stress. The higher the adhesive strength, the better the adhesiveness was evaluated. <Preheat and press temperature> The preheating and pressing temperatures for the materials constituting each layer (I) and / or layer (II) are shown below. Polyamide resin: 180℃ Polycarbonate resin: 180℃ Polyethylene terephthalate resin: 180℃ ABS resin: 90℃ Polyvinyl chloride resin: 90℃ Polyethylene: 120℃ Polypropylene: 120℃ Aluminum alloy: 200℃ SUS: 200℃ <Materials Constituting Layer (I) and / or Layer (II)> The following materials were used to form the layer (I) and / or the layer (II). Polyamide resin: Toray Plastics, L-001 Polycarbonate resin: Takiron, PC-1600 Polyethylene terephthalate resin: Takiron, 6010 ABS resin: Sumitomo Bakelite, EAR-003 Polyvinyl chloride resin: Kasai Sangyo Co., Ltd., Capilon K-5000 Polyethylene: Kyoei Resin Co., Ltd., 201H Polypropylene: Kyoei Resin Co., Ltd., PX-2 Aluminum alloy: A5052 SUS304:JIS,G,4305

[0082] [Hydrogenated conjugated diene copolymer] (denaturant) The following compounds were used as modifiers for producing the hydrogenated conjugated diene copolymers. Maleic anhydride (Fuso Chemical Co., Ltd.) 1,3-Dimethyl-2-imidazolidinone (Tokyo Chemical Industry Co., Ltd.)

[0083] (Preparation of hydrogenation catalyst) A hydrogenation catalyst used in the hydrogenation reaction of the hydrogenated conjugated diene copolymer was prepared by the following method. 1 L of dried and purified cyclohexane was placed in a nitrogen-substituted reaction vessel, and 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. With sufficient stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was allowed to react at room temperature for approximately 3 days to obtain a hydrogenation catalyst.

[0084] (adhesive manufacturing) As a component of the adhesives of the Examples and Comparative Examples, hydrogenated conjugated diene copolymers were prepared as follows. The physical properties of the hydrogenated conjugated diene copolymer are shown in Table 1 below. In the "Structure" column in Table 1, A represents a polymer block (A) mainly composed of vinyl aromatic monomer units, B represents a polymer block (B) mainly composed of conjugated diene monomer units, and C represents a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units.

[0085] <Preparation of modified hydrogenated conjugated diene copolymer (1)> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.14 parts by mass of n-butyllithium relative to 100 parts by mass of the total monomers and 0.25 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 15 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 30 minutes. Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 15 minutes. Thereafter, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted at 70°C for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction, thereby obtaining a modified conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the resulting modified conjugated diene copolymer in an amount of 70 ppm (Ti basis) per 100 parts by mass of the modified conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 1.5 hours. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the modified hydrogenated conjugated diene copolymer to obtain a modified hydrogenated conjugated diene copolymer (1). The modified hydrogenated conjugated diene copolymer (1) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 7.0×10 4 The vinyl bond content was 35%, the hydrogenation rate was 74%, and the modification rate was 80% (the number of modified groups per polymer chain was 0.80).

[0086] <Preparation of hydrogenated conjugated diene copolymer (2)> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.15 parts by mass of n-butyllithium relative to 100 parts by mass of the total monomers and 0.25 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 15 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 30 minutes. Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction, thereby obtaining a conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer in an amount of 70 ppm (Ti basis) per 100 parts by mass of the conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 2.0 hours. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene copolymer to obtain a hydrogenated conjugated diene copolymer (2). The hydrogenated conjugated diene copolymer (2) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 6.5×10 4 The vinyl bond content was 35% and the hydrogenation rate was 99%.

[0087] <Preparation of modified hydrogenated conjugated diene copolymer (2)-M> The hydrogenated conjugated diene copolymer (2) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation), and the mixture was fed into a twin-screw extruder with the temperature set to 150 to 210°C throughout the entire length of the extruder, and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene copolymer (2)-M. The obtained maleic anhydride-modified, hydrogenated conjugated diene copolymer (2)-M was titrated under the above-mentioned conditions, and the modification rate was found to be 1.1%.

[0088] <Preparation of modified hydrogenated conjugated diene copolymer (3)-M> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.16 parts by mass of n-butyllithium relative to 100 parts by mass of the total monomers and 0.25 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 15 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 30 minutes. Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction, thereby obtaining a conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer in an amount of 70 ppm (Ti basis) per 100 parts by mass of the conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 2.0 hours. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene copolymer to obtain a hydrogenated conjugated diene copolymer (3). The hydrogenated conjugated diene copolymer (3) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 6.5×10 4 The vinyl bond content was 35% and the hydrogenation rate was 99%. The hydrogenated conjugated diene copolymer (3) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation), and the mixture was fed into a twin-screw extruder with the temperature set to 150 to 210°C throughout the entire length of the extruder, and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene copolymer (3)-M. The obtained maleic anhydride-modified, hydrogenated conjugated diene copolymer (3)-M was titrated under the above-mentioned conditions, and the modification rate was found to be 1.1%.

[0089] <Preparation of modified hydrogenated conjugated diene copolymer (4)-M> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.067 parts by mass of n-butyllithium relative to 100 parts by mass of the total monomers and 0.8 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 10 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 87 parts by mass of butadiene was added and polymerization was carried out at 60° C. for 40 minutes. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 10 minutes. Thereafter, methanol was added to terminate the polymerization reaction, thereby obtaining a conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer in an amount of 70 ppm (Ti basis) per 100 parts by mass of the conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 2.0 hours. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene copolymer to obtain a hydrogenated conjugated diene copolymer (4). The hydrogenated conjugated diene copolymer (4) obtained as described above had a styrene content of 13% by mass and a weight-average molecular weight of 15.9×10 4The vinyl bond content was 70% and the hydrogenation rate was 99%. The hydrogenated conjugated diene copolymer (4) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation), and the mixture was fed into a twin-screw extruder with the temperature set to 150 to 210°C throughout the entire length of the extruder, and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene copolymer (4)-M. The obtained maleic anhydride-modified, hydrogenated conjugated diene copolymer (4)-M was titrated under the above-mentioned conditions, and the modification rate was found to be 0.6%.

[0090] <Preparation of hydrogenated conjugated diene copolymer (5)> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 20 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.040 parts by mass of n-butyllithium relative to 100 parts by mass of the total 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 15 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 32 parts by mass of butadiene and 48 parts by mass of styrene was added and polymerization was carried out at 70° C. for 40 minutes. Next, 0.5 mol of ethyl benzoate was added per 1 mol of n-butyllithium, and the mixture was reacted for 10 minutes at 70° C. Thereafter, methanol was added to terminate the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer in an amount of 90 ppm (Ti basis) per 100 parts by mass of the conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 2.0 hours to obtain a hydrogenated conjugated diene copolymer (5). The conjugated diene copolymer (5) obtained as described above had a styrene content of 65% by mass and a weight-average molecular weight of 18.9 × 10 4 The vinyl bond content was 25% and the hydrogenation rate was 98%.

[0091] <Preparation of modified hydrogenated conjugated diene copolymer (5)-M> The hydrogenated conjugated diene copolymer (5) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation), and the mixture was fed into a twin-screw extruder with the temperature set to 150 to 210°C throughout the entire length of the extruder, and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene copolymer (5)-M. The obtained maleic anhydride-modified, hydrogenated conjugated diene copolymer (5)-M was titrated under the above-mentioned conditions, and the modification rate was found to be 0.5%.

[0092] <Preparation of modified hydrogenated conjugated diene copolymer (6)> The same procedure as in the preparation of modified hydrogenated conjugated diene copolymer (1) was carried out, except that the amount of n-butyllithium was 0.18 parts by mass per 100 parts by mass of the total monomers. The modified hydrogenated conjugated diene copolymer (6) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 5.5×10 4 The vinyl bond content was 35%, the hydrogenation rate was 75%, and the modification rate was 80% (the number of modified groups per polymer chain was 0.80).

[0093] <Preparation of modified hydrogenated conjugated diene copolymer (7)> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution containing 44.5 parts by mass of styrene (concentration: 20% by mass) was added. Next, 0.091 parts by mass of n-butyllithium relative to 100 parts by mass of the total monomers and 0.8 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 30 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of butadiene was added and polymerization was carried out at 60° C. for 15 minutes. Next, a cyclohexane solution containing 44.5 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 30 minutes. Thereafter, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted at 70°C for 15 minutes. Thereafter, methanol was added to terminate the polymerization reaction, thereby obtaining a conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer in an amount of 70 ppm (Ti basis) per 100 parts by mass of the conjugated diene copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for approximately 2.0 hours. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the modified hydrogenated conjugated diene copolymer to obtain a modified hydrogenated conjugated diene copolymer (7). The modified hydrogenated conjugated diene block copolymer (7) obtained as described above had a styrene content of 85% by mass and a weight-average molecular weight of 7.0×10 4 The vinyl bond content was 35%, the hydrogenation rate was 75%, and the modification rate was 80% (the number of modified groups per polymer chain was 0.80).

[0094] [Table 1]

[0095] [Evaluation of Adhesion of Laminates (Examples 1 to 6, Comparative Examples 1 to 3)] The adhesive strength obtained by the above-mentioned adhesive property evaluation is shown in Table 2 below. The unit is N / cm. "-" indicates that the adhesive strength was so low that peeling occurred between the layers when the cut was made, and the adhesive strength could not be calculated.

[0096] [Table 2]

[0097] From Examples 1 to 6 and Comparative Examples 1 to 3, it became clear that by using a specific modified hydrogenated conjugated diene copolymer as an adhesive layer, a laminate having high adhesive strength can be obtained with a variety of materials. [Industrial Applicability]

[0098] The adhesive of the present invention exhibits high adhesive strength to a variety of materials, and laminates using the adhesive of the present invention have sufficient adhesive strength and are industrially applicable to a variety of applications, including housings for home appliances, vehicle components such as bumpers, door moldings, door mirrors and door undercovers, decorative molded articles such as containers, various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, backing adhesives for fixing various lightweight plastic molded products, backing adhesives for fixing carpets, backing adhesives for fixing tiles, power tools, toys, electrical and electronic equipment components, medical instruments, building materials and piping components, cutlery, household and cosmetic products, industrial parts, various hoses, various housings, various module cases, various power control unit components, writing instruments, robot hands, and medical instruments.

Claims

1. An adhesive containing a modified hydrogenated conjugated diene copolymer, The modified hydrogenated conjugated diene copolymer is a polymer block (A) mainly composed of vinyl aromatic monomer units; a polymer block (B) mainly composed of conjugated diene monomer units; and, (C) a polymer block having a vinyl aromatic monomer unit and a conjugated diene monomer unit; The modified hydrogenated conjugated diene copolymer has unsaturated bonds of conjugated diene monomer units hydrogenated, the content of vinyl aromatic monomer units in the modified hydrogenated conjugated diene copolymer is 10% by mass or more and 80% by mass or less; The adhesive, wherein the modified hydrogenated conjugated diene copolymer has at least one polar group.

2. The polar group is at least one selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group; The adhesive of claim 1 .

3. the polar group is an amino group; The adhesive of claim 1 .

4. Layer (I), layer (II), and A laminate having an adhesive layer (III) provided between the layer (I) and the layer (II), The layer (I) and the layer (II) The material is mainly made of at least one material selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass; The layer (III) is A layer comprising the adhesive according to any one of claims 1 to 3. Laminate.

5. the layer (I) and the layer (II) are mainly made of different materials, The main material in the layer (I) and the layer (II) is The material is any one selected from the group consisting of polyamide resins, polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polystyrene resins, polyolefin resins, metals, and glass; The laminate according to claim 4.

6. the layer (I) and the layer (II) are mainly made of different materials, The main material in the layer (I) and the layer (II) is The material is any one selected from the group consisting of polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, polyolefin resins, SUS, and aluminum alloys; The laminate according to claim 4.

7. The main material in the layer (I) is At least one material selected from the group consisting of polycarbonate resins, polyethylene terephthalate resins, ABS resins, polyvinyl chloride resins, SUS, and aluminum alloys; The main material of the layer (II) is It is a polyolefin resin. The laminate according to claim 4.

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