Block polymer, polymer composition, and adhesive

Abstract

To provide a block polymer capable of obtaining an adhesive which is excellent in initial adhesiveness, low adhesion-enhancing property, expandability and oil resistance and hardly generates adhesive residues on an adherend.SOLUTION: There is provided a block polymer which has 2 or more polymeric blocks A in which when a composition ratios (molar ratios) in a polymer of a structural unit represented by a formula (1), a structural unit represented by a formula (2), a structural unit represented by a formula (3) and a structural unit represented by a formula (4) are defined as p, q, r and s, respectively, a value α is 0.75 or more and a value β is 0.20 or less and has a functional group F containing at least one kind of element selected from a group consisting of nitrogen, silicon, oxygen and sulfur in a part or all of the terminals of 2 or more polymeric blocks. α=(p+(0.5×r)) / (p+q+(0.5×r)+s) (i), β=(p+q) / (p+q+(0.5×r)+s) (ii).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a block polymer, a polymer composition, and an adhesive.

Background Art

[0002] Conventionally, in order to protect the surfaces of various members such as optical members, metal plates, and synthetic resin plates from contamination and damage, the surfaces of the members have been covered with surface protection films (see, for example, Patent Document 1). Patent Document 1 discloses forming an adhesive layer of a surface protection film using a block copolymer having a polymer block in which the content of an aromatic alkenyl compound unit is 80% by mass or more, a polymer block having a conjugated diene unit and an aromatic alkenyl compound unit randomly, and a polymer block in which the content of the conjugated diene unit exceeds 80% by mass, and a hydrogenated product thereof.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] For an adhesive layer such as a surface protection film, adhesive properties such as initial adhesiveness to an adherend, a property of maintaining the adhesive force after sticking (low adhesive creep property), oil resistance, and difficulty in causing adhesive residue are required. However, it is difficult to develop a material that exhibits all of these adhesive properties in a well-balanced manner, and further improvement is required in adhesives.

[0005] The present invention has been made in view of the above problems, and a main object thereof is to provide a block polymer capable of obtaining an adhesive excellent in initial adhesiveness, low adhesive creep property, developability, and oil resistance, and having little adhesive residue on an adherend.

Means for Solving the Problems

[0006] The present invention provides the following block polymers, polymer compositions, and adhesives.

[0007] [1] When the composition ratios (molar ratios) of the structural units represented by the following formula (1), the structural units represented by the following formula (2), the structural units represented by the following formula (3), and the structural units represented by the following formula (4) in the polymer are p, q, r, and s, respectively, a value α represented by the following mathematical formula (i) is 0.75 or more, and a value β represented by the following mathematical formula (ii) is 0.20 or less, and having two or more polymer blocks A, and a functional group F containing at least one element selected from the group consisting of nitrogen, silicon, oxygen, and sulfur is provided at a part or all of the ends of the two or more polymer blocks A. A block polymer. α = (p + (0.5 × r)) / (p + q + (0.5 × r) + s) …(i) β = (p + q) / (p + q + (0.5 × r) + s) …(ii)

Chemical formula

[0008] [2] A polymer mixture containing the block polymer of [1] above and a block polymer having one polymer block A and the value α being 0.75 or more. [3] An adhesive obtained by using the block polymer of [1] above or the polymer mixture of [2] above.

Advantages of the Invention

[0009] According to the block polymer of the present invention, an adhesive excellent in initial adhesiveness, low adhesive creep property, developability, and oil resistance, and hardly leaving adhesive residue on the adherend (especially a polar adherend) can be obtained.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, matters related to the implementation of the present invention will be described in detail. In this specification, a numerical range described using "~" represents a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively.

[0011] ≪Block Polymer≫ The block polymer of the present disclosure (hereinafter, also referred to as "the present polymer") is a polymer including a polymer block A and a polymer block different from the polymer block A (hereinafter, also referred to as "polymer block B"). When the composition ratios (molar ratios) of the structural units represented by the following formula (1), the structural units represented by the following formula (2), the structural units represented by the following formula (3), and the structural units represented by the following formula (4) in the polymer are p, q, r, and s, respectively, the value α represented by the following mathematical formula (i) is 0.75 or more. Further, the polymer block A is a segment in which the value β represented by the following mathematical formula (ii) is 0.20 or less. α = (p + (0.5×r)) / (p + q + (0.5×r) + s) …(i) β = (p + q) / (p + q + (0.5×r) + s) …(ii)

Chemical Formula

[0012] <Polymer Block A> The polymer block A is a segment including a structural unit derived from 1,3-butadiene. The monomer constituting the polymer block A may be only 1,3-butadiene, or may further include a compound different from 1,3-butadiene (hereinafter, also referred to as "other monomer"). Examples of the other monomer include conjugated diene compounds different from 1,3-butadiene and aromatic vinyl compounds.

[0013] Specific examples of other monomers include, as conjugated diene compounds, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, β-farnesene, chloroprene, and the like. Among these, at least one selected from the group consisting of isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene is preferable, and isoprene is more preferable, in that an industrially usable polymer having excellent physical properties can be obtained. When a conjugated diene compound is used as another monomer, the conjugated diene compound can be used alone or in combination of two or more.

[0014] Further, examples of aromatic vinyl compounds include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine, and the like. Among these, styrene is particularly preferable. As the aromatic vinyl compound, one of these can be used alone or in combination of two or more.

[0015] Polymer block A is a segment mainly composed of structural units derived from 1,3-butadiene (hereinafter also referred to as "butadiene units"). Specifically, the proportion of butadiene units in polymer block A is preferably 75% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on all structural units derived from the monomers constituting polymer block A. When the butadiene units possessed by polymer block A are within the above range, an increase in the adhesiveness of the present polymer can be suppressed. Further, polymer block A can be made into a crystalline block segment having a structure similar to that of low-density polyethylene (LDPE) by hydrogenation. In this case, it is suitable when the present polymer is used for adhesive applications in that an increase in adhesiveness can be suppressed, the spreadability of the adhesive can be improved, and the oil resistance can be improved.

[0016] A preferred embodiment of the polymer block A is a segment obtained by polymerizing a monomer containing 1,3-butadiene and then hydrogenating it (hereinafter also referred to as "hydrogenation"). The vinyl bond content of the polymer block A is 20 mol% or less. When the vinyl bond content of the polymer block A exceeds 20 mol%, the present polymer tends to become too soft, leading to a decrease in mechanical properties, processability, and adhesion performance (especially adhesion promotion). From the above viewpoints, the vinyl bond content of the polymer block A is preferably 18 mol% or less, more preferably 16 mol% or less. Also, the vinyl bond content of the polymer block A is, for example, 5 mol% or more.

[0017] In the present specification, the "vinyl bond content" is a value indicating the ratio of the structural units having 1,2-bonds to all the structural units derived from butadiene possessed by the polymer before hydrogenation, 1 and is a value measured by an H-NMR apparatus. The vinyl bond content of the polymer is represented as β in the above formula (ii). For example, when β is 0.20, it means that the vinyl bond content of the polymer (or polymer block) is 20 mol%.

[0018] Some or all of the terminals of two or more polymer blocks A of the present polymer have a functional group F containing at least one element selected from the group consisting of nitrogen, silicon, oxygen, and sulfur. Thereby, a block polymer excellent in adhesion performance can be obtained.

[0019] Specific examples of the functional group F include, for example, a primary amino group, a secondary amino group, a tertiary amino group, a nitrogen-containing group in which two hydrogen atoms of the primary amino group are substituted by two protecting groups, a nitrogen-containing group in which one hydrogen atom of the secondary amino group is substituted by one protecting group, an imino group, a nitrogen-containing heterocyclic group (for example, a group having a heterocycle such as a pyridine ring or an imide ring), a hydroxyl group, an oxygen-containing group in which one hydrogen atom of the hydroxyl group is substituted by one protecting group, a thiol group, a sulfur-containing group in which one hydrogen atom of the thiol group is substituted by one protecting group, a hydrocarbyloxysilyl group, and the like. The functional group F is preferably a nitrogen-containing functional group (nitrogen-containing group) because it has a high effect of improving the adhesiveness to a highly polar adherend and a high effect of improving the developability by suppressing excessive adhesion to a low-polarity adherend. It is particularly preferable to have at least one selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and an imide group. Further, from the viewpoint of ensuring a reaction point with a modifier (post-modifier) and a crosslinking agent that can be used in a subsequent reaction and improving heat resistance, solvent resistance, suppression of glue residue, and contamination of the adherend by residues, it is preferable that the polymer has at least one of a primary amino group and a secondary amino group at a part or all of the ends of the polymer block A, and it is particularly preferable to have a plurality of at least one of a primary amino group and a secondary amino group in one molecule.

[0020] The end of the polymer block A on the side having the functional group F preferably constitutes the end of the present polymer. That is, the polymer block A is disposed at the end of the present polymer, and it is preferable that the end of the polymer has the functional group F. By introducing the functional group F into a part or all of the ends of the block polymer, the adhesion performance can be improved.

[0021] <Polymer block B> The polymer block B is preferably a segment containing a structural unit derived from a conjugated diene compound. Examples of the conjugated diene compound constituting the polymer block B include the same compounds as the conjugated diene compounds (including 1,3-butadiene) exemplified in the description of the polymer block A. Among these, at least one selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and β-farnesene is preferable in that a polymer that can be industrially utilized and exhibits excellent physical properties can be obtained. At least one selected from the group consisting of 1,3-butadiene and isoprene is more preferable, and 1,3-butadiene is particularly preferable. As the conjugated diene compound, one of these can be used alone or in combination of two or more.

[0022] The vinyl bond content of the polymer block B (i.e., the value β represented by the above formula (ii)) is preferably higher than that of the polymer block A. Specifically, the vinyl bond content of the polymer block B is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 45 mol% or more, and particularly preferably 50 mol% or more. When the vinyl bond content of the polymer block B is within the above range, it is suitable in terms of being able to sufficiently increase the adhesion performance (particularly, peel strength and tackiness) of the present polymer, and being able to lower the solution viscosity when the polymer is dissolved in an organic solvent, thereby improving productivity and processability. Also, the vinyl bond content of the polymer block B is, for example, 90 mol% or less.

[0023] The polymer block B may be a segment consisting only of a conjugated diene compound, but may further contain a structural unit derived from a monomer copolymerizable with the conjugated diene compound (hereinafter also referred to as a "conjugated diene unit") together with the structural unit derived from the conjugated diene compound.

[0024] In the polymer block B, the monomer copolymerized with the conjugated diene compound is not particularly limited, but among them, an aromatic vinyl compound is preferable. When the polymer block B has a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as "aromatic vinyl unit"), it is suitable in terms of improving the developability of the adhesive and improving the vibration damping characteristics when the present polymer is used for adhesive applications. In the polymer block B, examples of the monomer that provides the aromatic vinyl unit include the same compounds as the aromatic vinyl compounds exemplified in the description of the polymer block A. Among them, styrene is particularly preferable.

[0025] In the polymer block B, the proportion of the conjugated diene unit is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 65% by mass or more based on all the structural units derived from the monomers constituting the polymer block B. When the conjugated diene unit contained in the polymer block B is within the above range, it is suitable in that the adhesive strength of the present polymer can be increased and an adhesive with less glue residue can be obtained.

[0026] When the polymer block B contains an aromatic vinyl unit, the proportion of the aromatic vinyl unit in the polymer block B is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less based on all the structural units derived from the monomers constituting the polymer block B. When the proportion of the aromatic vinyl unit in the polymer block B is within the above range, it is preferable in terms of improving the vibration damping characteristics of the composition containing the present polymer and further improving the developability of the adhesive when applied to the adhesive.

[0027] When the polymer block B is a copolymer of a conjugated diene compound and another monomer (preferably an aromatic vinyl compound), the distribution of the other monomer in the polymer block B is not particularly limited, and for example, it can be random, tapered, partially blocky, or any combination thereof. Among these, the random form is preferable in that the effect of introducing the other monomer can be sufficiently obtained by introducing the other monomer throughout the polymer block B.

[0028] <Block Structure> As long as this polymer has two or more polymer blocks A and two or more types of polymer blocks including polymer block A, the number of blocks, the arrangement of each block, the polymer structure, etc. are not particularly limited. This polymer may be a linear polymer having two or more polymer blocks A and one or more polymer blocks B, or may be a non-linear polymer. Among these, in terms of being able to obtain a block polymer with excellent adhesion performance, and in the reaction with a cross-linking agent capable of reacting with the functional group F, a non-linear polymer is preferable and a radial polymer (also referred to as a star polymer) is more preferable in that a network structure can be formed more efficiently, thereby improving heat resistance, solvent resistance, suppression of glue residue, and stain resistance due to low residue. In particular, this polymer preferably has a structure in which two or more polymer chains having polymer block A are bonded to the partial structure E derived from the coupling agent.

[0029] Preferable specific examples of this polymer include block polymers having a structure represented by the following formula (5). (P 1 )n-X 1 …(5) (In formula (5), P 1 is a polymer chain having polymer block A. X 1 is a partial structure derived from a coupling agent (hereinafter, also referred to as "partial structure E"). n is an integer of 2 or more.)

[0030] In the above formula (5), P 1 is preferably linear. As P 1 , for example, an AB-type diblock body composed of polymer block A / polymer block B, an ABA-type triblock body composed of polymer block A / polymer block B / polymer block A, a BAB-type triblock body composed of polymer block B / polymer block A / polymer block B, etc. can be mentioned. Also, P 1It may further have a polymer block different from the polymer block A and the polymer block B, and may be a polymer chain having 4 or more blocks. Among these, a polymer exhibiting excellent adhesive performance with a smaller number of blocks can be produced, and in terms of excellent productivity, P 1 is preferably an AB-type diblock.

[0031] From the viewpoint of ensuring the processability of the present polymer, n is preferably an integer of 2 to 10. In terms of obtaining a polymer with further improved adhesive performance (particularly, suppression of the increase in peel strength and adhesiveness), n is preferably 3 or more, and particularly preferably 4 or more. In the above formula (5), a polymer in which n is 4 or more, that is, a block polymer having a structure in which 4 or more polymer chains P 1 are bonded to the partial structure E is particularly preferable because it has a high effect of improving the adhesive force, can form a network structure more efficiently with a crosslinking agent, and can be expected to have an effect of improving solvent resistance and heat resistance.

[0032] In the present polymer, the ratio of the polymer block A to the total amount (100% by mass) of the polymer block A and the polymer block B is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Also, the ratio of the polymer block A is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less, based on the total amount of the polymer block A and the polymer block B. When the ratio of the polymer block A is 10% by mass or more, the present polymer does not become too soft, the handleability of the present polymer can be improved, and good solvent resistance can be imparted, which is preferable. Also, when the ratio of the polymer block A is 80% by mass or less, it is preferable in terms of sufficiently ensuring the mechanical properties of the present polymer.

[0033] This polymer has a value α represented by the above formula (i) of 0.75 or more. In this polymer, when the value α is less than 0.75, the tackiness of the polymer tends to increase, and the oil resistance tends to decrease. From the viewpoint of obtaining a polymer showing good suppression of tack increase and oil resistance, the value α in this polymer is preferably 0.80 or more, more preferably 0.85 or more, still more preferably 0.90 or more, even more preferably 0.95 or more, and particularly preferably 97% or more. Also, the value α in this polymer is, for example, 99% or less in order to ensure the peel strength and tackiness of the polymer.

[0034] In addition, in this specification, the value α represented as the value α by the above formula (i) represents the hydrogenation rate of the polymer. For example, when α is 0.75, it means that the hydrogen addition rate of the polymer is 75%. The "hydrogen addition rate" is 1 a value measured by an H-NMR apparatus.

[0035] <Manufacture of Block Polymer> The method for producing the block polymer is not particularly limited. As the polymerization method to be used, any of a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, etc. may be used, but the solution polymerization method is particularly preferred. Also, as the polymerization form, either a batch type or a continuous type may be used. When the solution polymerization method is used, as an example of a specific polymerization method, in an organic solvent, a polymer chain P having a polymer block A is produced by polymerizing a monomer in the presence of a polymerization initiator and, if necessary, a vinyl content regulator (randomizer) (polymerization step), then a coupling agent is added to carry out a coupling reaction (coupling step), and thereafter, a hydrogenation reaction is carried out (hydrogenation step). 1 The method includes producing (polymerization step), then adding a coupling agent to carry out a coupling reaction (coupling step), and thereafter, carrying out a hydrogenation reaction (hydrogenation step).

[0036] (Polymerization Step) As the polymerization initiator, an alkali metal compound is preferably used. Specific examples of the alkali metal compound include alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, t-butyllithium; 1,4-dilithiobutane, phenyllithium, stilbenelithium, naphthyllithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium, naphthylsodium, naphthylpotassium, ethoxypotassium, etc. Among these, the alkali metal compound used as the polymerization initiator is preferably a lithium compound.

[0037] The polymerization reaction is preferably carried out in the presence of a compound (R) obtained by mixing the above alkali metal compound and a compound having a functional group F (hereinafter also referred to as "starting-end modifier"). By carrying out the polymerization in the presence of the compound (R), a functional group F can be introduced at the polymerization initiation terminal of the polymer chain P 1 thereof.

[0038] Compound (R) is preferably a reaction product of a lithium compound such as alkyllithium and a compound having a nitrogen atom. The starting-end modifier is preferably a secondary amine compound, and examples thereof include alkylamines, alicyclic amines, aromatic amines, and heterocyclic amines. Specific examples thereof include dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N,N'-dimethyl-N'-trimethylsilyl-1,6-diaminohexane, piperidine, pyrrolidine, hexamethyleneimine, heptamethyleneimine, dicyclohexylamine, N-methylbenzylamine, di-(2-ethylhexyl)amine, diallylamine, morpholine, N-(trimethylsilyl)piperazine, N-(tert-butyldimethylsilyl)piperazine, 1,3-ditrimethylsilyl-1,3,5-triazinane, and the like. Among these, for the purpose of improving the reactivity with a post-modifier (such as maleic anhydride) or a cross-linking agent (such as a polyfunctional epoxy compound), a compound having a group in which at least one of a primary amino group and a secondary amino group is protected with a silyl compound or the like can be preferably used.

[0039] When polymerization is carried out in the presence of compound (R), compound (R) may be prepared by premixing an alkali metal compound and a starting-end modifier, and the prepared compound (R) may be added to the polymerization system for polymerization. Alternatively, an alkali metal compound and a starting-end modifier may be added to the polymerization system, and compound (R) may be prepared by mixing the two in the polymerization system for polymerization. The amount of the polymerization initiator used (the total amount when two or more are used) is preferably 0.01 to 20 mmol, more preferably 0.05 to 15 mmol, per 100 g of the monomer used for the synthesis of the polymer.

[0040] The vinyl content regulator is used for the purpose of adjusting the vinyl bond content in the polymer, etc. Examples of the vinyl content regulator include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(tetrahydrofuryl)propane, 2-(2-ethoxyethoxy)-2-methylpropane, triethylamine, pyridine, N-methylmorpholine, and tetramethylethylenediamine, etc. As the vinyl content regulator, one kind can be used alone or two or more kinds can be used in combination.

[0041] As the organic solvent used for polymerization, any organic solvent that is inert to the reaction can be used. For example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. can be used. Among these, hydrocarbons having 3 to 8 carbon atoms are preferred, and specific examples thereof include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentyne, 2-pentyne, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1-pentene, 2-pentene, cyclohexene, etc. Note that as the organic solvent, one kind can be used alone or two or more kinds can be used in combination.

[0042] When carrying out solution polymerization, from the viewpoint of maintaining the balance between productivity and ease of polymerization control, the monomer concentration in the reaction solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. The temperature of the polymerization reaction is preferably -30°C to 150°C. The polymerization may be carried out while controlling the temperature to be constant, or may be carried out under heating without heat removal. Further, the polymerization reaction is preferably carried out under a pressure sufficient to keep the monomer substantially in the liquid phase. Such pressure can be obtained by methods such as pressurizing the inside of the reactor with a gas inert to the polymerization reaction.

[0043] The method of using the reaction product of the above polymerization reaction as a block polymer may be any method. When producing a block polymer having a polymer block A and a polymer block B, from the viewpoint of productivity, first, in the presence of a polymerization initiator and an initiator-end modifier, a monomer containing a conjugated diene compound is polymerized to produce one of the polymer block A and the polymer block B (hereinafter, also referred to as "the first segment"). Next, in the presence of the first segment, a monomer containing a conjugated diene compound is polymerized to produce the other segment (hereinafter, also referred to as "the second segment"). Thereby, a block polymer in which a functional group F is introduced at the initiation terminal of the first segment can be obtained. Note that the boundary of each polymer block may not be clearly distinguished. In this polymer, by using the first segment as the polymer block A, a block polymer excellent in adhesive performance can be obtained.

[0044] In addition, the vinyl bond content of each polymer block can be adjusted by the amount of the vinyl content regulator used. More specifically, first, in the presence of a polymerization initiator, an initiator-end modifier, and a vinyl content regulator used as necessary, a monomer containing 1,3-butadiene is polymerized to produce a low-vinyl polybutadiene block that becomes the polymer block A. Subsequently, a monomer containing a conjugated diene compound and a vinyl content regulator are added to the reaction system and polymerization is carried out. Thereby, a block polymer having a plurality of polymer blocks with different vinyl bond contents can be obtained.

[0045] (Coupling step) Next, the block polymer obtained by the above polymerization step (that is, the polymer chain constituting this polymer) is reacted with a coupling agent. The coupling agent used in the production of this polymer is not particularly limited, and a coupling agent known in the production of polymers can be appropriately used. The coupling agent is preferably a polyfunctional coupling agent having two or more reaction sites with the polymer chain. The number of reaction sites of the coupling agent is preferably three or more, more preferably four or more.

[0046] Specific examples of the coupling agent include, for example, 1,2-dibromoethane, methyldichlorosilane, dimethyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene-1,2,4-triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermane, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4-chloromethylbenzene, bis(trichlorosilyl)ethane, and the like.

[0047] Also, as the coupling agent, a compound having a functional group F containing at least one element selected from the group consisting of nitrogen, silicon, oxygen, and sulfur and having two or more reaction sites with the polymer chain obtained by the above polymerization step (hereinafter, also referred to as "terminal modifier") can be used. Specific examples of the functional group F possessed by the terminal modifier include the same groups as the specific examples of the functional group F described in the above polymerization step.

[0048] Specific examples of such terminal modifiers include, for example, nitrogen-containing alkoxysilane compounds described in JP-A-2014-177519, JP-A-2016-079217, and WO 2017 / 221943; glycidyl group-containing polysiloxanes described in WO 2017 / 090421, and the like. Among these, a polyfunctional coupling agent having a functional group containing nitrogen can be preferably used. When a nitrogen-containing polyfunctional coupling agent is used, it is suitable in that a polymer in which high adhesiveness and suppression of the increase in tackiness are improved in a well-balanced manner can be produced.

[0049] The reaction between the block polymer obtained by the above polymerization step and the coupling agent is preferably carried out as a solution reaction. The usage ratio of the coupling agent (the total amount when two or more kinds are used) is preferably 0.01 mol or more, more preferably 0.05 mol or more, per 1 mol of the metal atom involved in the polymerization of the polymerization initiator, from the viewpoint of allowing the coupling reaction to proceed sufficiently. Also, the usage ratio of the coupling agent is preferably less than 2.0 mol, more preferably less than 1.5 mol, per 1 mol of the metal atom involved in the polymerization of the polymerization initiator, from the viewpoint of avoiding a decrease in processability and excessive addition. Note that as the coupling agent, one kind may be used alone, or two or more kinds may be used in combination.

[0050] The temperature of the above reaction is usually the same as that of the polymerization reaction, and is preferably -30°C to 150°C. When the reaction temperature is low, the viscosity of the polymer after coupling tends to increase easily. When the reaction temperature is high, the polymerization terminal tends to be deactivated easily. The reaction time is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.

[0051] In the coupling reaction for obtaining the present polymer, the coupling rate is preferably 40% or more, more preferably 50% or more, still more preferably 70% or more, in terms of improving the oil resistance and adhesion of the composition containing the present polymer and suppressing the advancement, and in terms of being able to efficiently form a network structure by reaction with a crosslinking agent. Also, the coupling rate is preferably 90% or less, more preferably 85% or less, from the viewpoint of obtaining a polymer composition with good processability. Here, in this specification, the "coupling rate" means the ratio of the polymer bonded via the coupling agent among the polymers used in the reaction with the coupling agent (that is, the polymer chains P 1 ) that will constitute the present polymer. The coupling rate can be calculated from the peak area ratio of the GPC curve obtained using gel permeation chromatography (GPC).

[0052] When the coupling rate is less than 100%, as the present polymer, a polymer having a structure in which two or more polymer chains P are bonded to a partial structure E derived from a coupling agent (hereinafter, also referred to as "first polymer"), and a polymer having only one polymer chain P (hereinafter, also referred to as "second polymer") are included in the polymer mixture. This polymer mixture may be used as it is in the following hydrogenation step, or may be used in the following hydrogenation step after purification. 1 A polymer having a structure in which two or more polymer chains P are bonded to a partial structure E derived from a coupling agent (hereinafter, also referred to as "first polymer"), and a polymer having only one polymer chain P (hereinafter, also referred to as "second polymer") are included in the polymer mixture. This polymer mixture may be used as it is in the following hydrogenation step, or may be used in the following hydrogenation step after purification. 1 A polymer mixture containing a polymer having a structure in which two or more polymer chains P are bonded to a partial structure E derived from a coupling agent (hereinafter, also referred to as "first polymer") and a polymer having only one polymer chain P (hereinafter, also referred to as "second polymer") is obtained. This polymer mixture may be used as it is in the following hydrogenation step, or may be used in the following hydrogenation step after purification.

[0053] (Hydrogenation Step) In this step, the block polymer obtained by the above coupling step is hydrogenated. The method and conditions of the hydrogenation reaction can be any method and conditions as long as a block polymer with a desired hydrogenation rate can be obtained. Specific examples of the hydrogenation method include a method using a catalyst mainly composed of an organometallic compound of titanium as a hydrogenation catalyst, a method using a catalyst composed of an organic compound of iron, nickel, cobalt and an organometallic compound such as alkylaluminum, a method using an organic complex of an organometallic compound such as ruthenium and rhodium, and a method using a catalyst in which metals such as palladium, platinum, ruthenium, cobalt and nickel are supported on a carrier such as carbon, silica and alumina. Among various methods, a method of using a homogeneous catalyst composed of an organometallic compound of titanium alone or an organometallic compound of titanium and an organometallic compound of lithium, magnesium or aluminum (see, for example, Japanese Patent Publication No. 63-4841 and Japanese Patent Publication No. 1-37970) and hydrogenating under mild conditions of low pressure and low temperature is industrially preferable, and the hydrogenation selectivity to the double bond of butadiene is also high and suitable.

[0054] The hydrogenation of the block polymer is preferably carried out using a solvent that is inert to the catalyst and soluble to the block polymer. Preferred solvents include aliphatic hydrocarbons (e.g., n-pentane, n-hexane, n-octane), alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane), aromatic hydrocarbons (e.g., benzene, toluene), ethers (e.g., diethyl ether, tetrahydrofuran) alone or mixtures mainly composed of these.

[0055] The hydrogenation reaction is generally carried out by maintaining the block polymer at a predetermined temperature under hydrogen or an inert atmosphere, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas to pressurize it to a predetermined pressure. The inert atmosphere means an atmosphere that does not react with the participants in the hydrogenation reaction, and examples thereof include helium, neon, argon, etc. Air and oxygen may oxidize the catalyst and cause deactivation of the catalyst. Also, nitrogen may act as a catalyst poison during the hydrogenation reaction and may reduce the hydrogenation activity. Therefore, it is preferable that the inside of the hydrogenation reactor is an atmosphere of hydrogen gas alone.

[0056] The hydrogenation reaction process for obtaining the block polymer can be used in any of a batch process, a continuous process, or a combination thereof. When using a titanocene diaryl-based compound as the hydrogenation catalyst, it may be added directly to the reaction solution as it is, or added as a solution in an inert organic solvent. The addition amount of the catalyst is, for example, 0.02 to 20 millimoles per 100 g of the block polymer before hydrogenation.

[0057] From the viewpoint of suppressing the increase in the adhesiveness of the polymer, improving the developability and solvent resistance, the hydrogenation rate of the present polymer is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, further preferably 90% or more, even more preferably 95% or more, and particularly preferably 97% or more. Also, from the viewpoint of ensuring the peel strength and tackiness of the polymer, the hydrogenation rate of the present polymer is preferably 99% or less.

[0058] After hydrogenation, if necessary, remove the catalyst residue, or add a phenolic or amine-based antioxidant, and then isolate the hydrogenated conjugated diene-based polymer (i.e., the present polymer) from the polymer solution. The isolation of the polymer can be carried out, for example, by adding acetone or alcohol to the polymer solution to precipitate it, or by charging the polymer solution into hot water with stirring and distilling off the solvent.

[0059] For this polymer, the weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 5.0×10 4 ~7.0×10 5 . When Mw is 5.0×10 4 or more, it has excellent mechanical properties and is less likely to cause glue residue when used as an adhesive. Also, when Mw is 7.0×10 5 or less, it is preferable in that the fluidity of this polymer can be sufficiently ensured, the molding processability can be improved, and sufficient heat resistance and solvent resistance can be ensured by the reaction with a crosslinking agent. The Mw of this polymer is more preferably 7.0×10 4 or more, and even more preferably 1.0×10 5 or more. Also, the Mw of this polymer is more preferably 6.5×10 5 or less. Note that the weight-average molecular weight of the polymer referred to here represents the weight-average molecular weight based on all peaks (total weight-average molecular weight).

[0060] (Post-modification step) Regarding the block polymer after the hydrogenation reaction, it may be used as it is for the desired application, but a further modification treatment may be performed on the block polymer after the hydrogenation reaction (post-modification step). Such a modification treatment is preferable in that it can further improve the suppression of the increase in adhesiveness and the spreadability of this polymer. In particular, in a polymer in which a primary amine or a secondary amine is introduced at the terminal by the modification treatment, the modification rate of the modifier (hereinafter also referred to as the "post-modifier") in the post-modification step is improved, and the generation of residues of the post-modifier can be suppressed. For this reason, it is preferable in that contamination of the adherend due to re-peeling and diffusion of the contamination component to the adherend due to permanent adhesion can be suppressed.

[0061] As the post-modifying agent, a compound having at least one functional group selected from the group consisting of an alkoxysilyl group, a carboxy group, an amino group, a hydroxy group, an epoxy group, and a group derived from an acid anhydride can be preferably used. Specific examples of such post-modifying agents include dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, hydroxymethyltriethoxysilane, vinylbenzyldiethylamine, vinylbenzyldimethylamine, 1-glycidyl-4-(2-pyridyl)piperazine, 1-glycidyl-4-phenylpiperazine, 1-glycidyl-4-methylpiperazine, 1-glycidyl-4-methylhomopiperazine, 1-glycidylhexamethyleneimine, and tetraglycidyl-1,3-bis(aminomethyl)cyclohexane. Further, examples of the post-modifying agent include unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride. Note that the post-modifying agent may be used alone or in combination of two or more kinds.

[0062] The reaction between the hydrogenated block polymer and the post-modifying agent is carried out, for example, by melting the hydrogenated block polymer using an extruder or the like, preferably in the presence of a catalyst (for example, a radical generator such as an organic peroxide). In the reaction between the hydrogenated block polymer and the post-modifying agent after the hydrogenation reaction, the usage ratio of the post-modifying agent is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the block polymer. From the viewpoint of avoiding excessive addition while allowing the reaction to proceed sufficiently, the usage ratio of the post-modifying agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the block polymer. Further, the temperature during the above reaction is, for example, 100 to 300°C.

[0063] Further, a composition containing a hydrogenated block polymer and a crosslinking agent may be reacted while applying shear deformation, thereby crosslinking the hydrogenated block polymer. By forming a crosslinked structure in the hydrogenated block copolymer, further improvement in solvent resistance and mechanical strength can be achieved. As the crosslinking agent, a compound having two or more functional groups capable of reacting with the functional group F can be preferably used. Examples of such crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, aldehyde-based crosslinking agents, amine-based crosslinking agents, chelate-based crosslinking agents, carbodiimide-based crosslinking agents, as well as hydroxyl group-containing compounds, acid compounds, acid anhydrides, radical generators, and the like.

[0064] Examples of the isocyanate-based crosslinking agents include aromatic isocyanate-based crosslinking agents such as tolylene diisocyanate-based crosslinking agents like 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, xylylene diisocyanate-based crosslinking agents like 1,3-xylylene diisocyanate, diphenylmethane-based crosslinking agents like diphenylmethane-4,4-diisocyanate, and naphthalene diisocyanate-based crosslinking agents like 1,5-naphthalene diisocyanate; alicyclic isocyanate-based crosslinking agents such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane, and norbornane diisocyanate; aliphatic isocyanate-based crosslinking agents such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and adducts, biuret bodies, isocyanurate bodies, etc. of the above isocyanate-based compounds.

[0065] Examples of the epoxy crosslinking agent include bisphenol A-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, and diglycerol polyglycidyl ether.

[0066] Examples of the aziridine-based crosslinking agent include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), and N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide).

[0067] Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexaptoxymethylmelamine, hexapentyloxymethylmelamine, hexahexyloxymethylmelamine, melamine resins, and the like.

[0068] Examples of the aldehyde crosslinking agent include glyoxal, malondialdehyde, succindialdehyde, maleic dialdehyde, glutaric dialdehyde, formaldehyde, acetaldehyde, and benzaldehyde.

[0069] Examples of the amine-based crosslinking agent include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resins, and polyamides.

[0070] Examples of the above metal chelate crosslinking agents include acetylacetone and acetoacetyl ester coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, palladium, chromium, and zirconium.

[0071] Examples of the above carbodiimide crosslinking agents include polyfunctional carbodiimide compounds and polymer-type carbodiimide compounds.

[0072] Examples of the above hydroxyl group-containing compounds include polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols.

[0073] Examples of the above polyfunctional crosslinking agents containing carboxy groups include aromatic dicarboxylic acids such as σ-phthalic acid, isophthalic acid, terephthalic acid, 1,4-dimethylterephthalic acid, 1,3-dimethylisophthalic acid, 5-sulfo-1,3-dimethylisophthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, or phenylindanedicarboxylic acid; aromatic dicarboxylic anhydrides such as phthalic anhydride, 1,8-naphthalenedicarboxylic anhydride, or 2,3-naphthalenedicarboxylic anhydride; alicyclic dicarboxylic acids such as hexahydrophthalic acid; alicyclic dicarboxylic anhydrides such as hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 1,2-cyclohexanedicarboxylic anhydride; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, or itaconic acid.

[0074] Examples of the acid anhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfone tetracarboxylic dianhydride, diphenylsulfide tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, and the like.

[0075] The radical generator is used to generate radicals by irradiating ultraviolet rays such as heat or ultraviolet rays when producing the pressure-sensitive adhesive layer that constitutes a part of the pressure-sensitive adhesive film. Radicals can be generated to crosslink the present polymer. As the radical generator, a photo radical generator that generates radicals by irradiating light such as ultraviolet rays is preferable. Specific examples of the photo radical generator include hydroxyketones, benzyldimethylketals, aminoketones, acylphosphine oxides, benzophenones, and the like. These photo radical generators can be used alone or in combination of two or more.

[0076] The radical generator may be an oligomer-type photo radical generator. The oligomer-type photo radical generator is a low molecular weight polymer of a monomer having a functional group capable of generating radicals by irradiating light such as ultraviolet rays. Since such an oligomer-type photo radical generator has a plurality of radical generation points in one molecule, it is hardly affected by crosslinking inhibition by oxygen, can be crosslinked with a small amount, does not scatter even in a solvent-free hot melt state when applied to a substrate, and is not extracted from the polymer. It is preferably used in terms of the above points.

[0077] Specific examples of the oligomer-type photo radical generator include an oligomer obtained by polymerizing acrylated benzophenone (manufactured by UCB, trade name "Ebecryl P36"), an oligomer obtained by polymerizing a reaction product of the primary hydroxyl group of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF, trade name "Irgacure 2959") and 2-isocyanatoethyl methacrylate, a 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer (manufactured by Lamberti, trade name "Esacure KIP150"), and the like. The molecular weight of these oligomer-type photo radical generators is preferably about 50,000 or less.

[0078] Note that as the crosslinking agent, one kind may be used alone, or two or more kinds may be used in combination. The amount of the crosslinking agent used can be appropriately determined according to the performance required for the target final composition. The amount of the crosslinking agent used is usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the present polymer. The reaction between the present polymer and the crosslinking agent may be carried out in the presence of a curing catalyst as necessary.

[0079] ≪Adhesive≫ Since the present polymer has excellent adhesive performance, it is suitable for use as an adhesive. The adhesive obtained by using the present polymer may contain only one kind of the present polymer, or may contain two or more kinds. Further, the polymer mixture of the first polymer and the second polymer described above can also be used as an adhesive material. According to the polymer mixture of the first polymer and the second polymer, the polymer obtained by a series of operations of the above-described polymerization step, coupling step, and hydrogenation step can be used as it is, and moreover, since it exhibits excellent adhesive performance, it has high productivity and is industrially advantageous.

[0080] In the adhesive containing the present polymer (hereinafter also referred to as "the present adhesive"), from the viewpoint of exhibiting excellent adhesive performance, the content ratio of the present polymer (i.e., the first polymer) is preferably 10 to 90% by mass with respect to the total amount (100% by mass) of the adhesive. The ratio of the present polymer is more preferably 20% by mass or more, and even more preferably 40% by mass or more with respect to the total amount of the adhesive. Also, the ratio of the first polymer is more preferably 85% by mass or less, and even more preferably 80% by mass or less with respect to the total amount of the adhesive.

[0081] In addition, from the viewpoint of exhibiting excellent adhesive performance, the total ratio of the first polymer and the second polymer contained in the present adhesive is preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more with respect to the total amount of the present adhesive. Note that the present polymer blended in the present adhesive may be only one kind or two or more kinds.

[0082] The present adhesive may be composed only of the present polymer, but may further contain components different from the present polymer (hereinafter also referred to as "other components"). Examples of other components include, in addition to the second polymer, tackifiers. By blending a tackifier into the present adhesive, the initial adhesiveness of the adhesive can be improved.

[0083] As the tackifier, for example, petroleum resins (such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, alicyclic copolymers, etc.), coumarone-indene resins, terpene resins, terpene phenol resins, rosin resins, (alkyl)phenol resins, xylene resins, or hydrogenated products thereof, etc., which are generally used in adhesive applications, can be used. As the tackifier, only one kind may be used, or two or more kinds may be used in combination.

[0084] In addition, as other components, in addition to the above, for example, polyolefin resins, antioxidants, ultraviolet absorbers, colorants, light stabilizers, thermal polymerization inhibitors, defoamers, leveling agents, antistatic agents, surfactants, storage stabilizers, anti-aging agents, flame retardants, various fillers, etc. can be mentioned. In this adhesive, the blending ratio of other components can be appropriately set according to each component within the range that does not impair the effects of the present disclosure.

[0085] Since this polymer is excellent in various properties such as initial adhesiveness, low adhesive build-up property, developability, paste residue suppression property, solvent resistance, etc., it can be used in various applications. Specifically, it can be used as the adhesive layer of a surface protection film, the adhesive layer of an adhesive film for a structure, a modifier for a resin composition, and also as a molded article. Furthermore, this polymer is excellent in vibration damping properties and can be used in various applications such as vibration damping materials, vibration damping films, and vibration damping sheets.

[0086] In addition, according to the present disclosure, a laminate having an X layer containing this polymer and a Y layer laminated on at least one surface of the X layer is also provided. As such a laminate, for example, laminated glass is suitable. Specifically, by using the above X layer as an interlayer film for laminated glass and the above Y layer as a glass layer and laminating these to form laminated glass, not only excellent vibration damping properties but also excellent sound insulation properties can be expected. In addition, as the Y layer, in addition to the glass layer, it can be appropriately selected according to various applications. For example, a laminate having a layer containing a thermoplastic resin other than this polymer as the Y layer can be mentioned. Examples of such thermoplastic resins include polyvinyl acetal resins, ionomers, ethylene-vinyl acetate copolymers, urethane resins, polyamide resins, etc.

[0087] Other applications of this polymer include, for example, the following applications. (1) Pellets, veils, sound-absorbing materials, sound-insulating materials, dam rubbers, shoe sole materials, floor materials, weather strips, floor mats, dash insulators, roof linings, door panels, engine head covers, door hole seals, fender liners, etc. (2) Various products in the automotive field: For example, cooling parts such as thermostat housings, radiator tanks, radiator hoses, water outlets, water pump housings, rear joints, etc.; intake and exhaust system parts such as intercooler tanks, intercooler cases, turbo duct pipes, EGR cooler cases, resonators, throttle bodies, intake manifolds, tail pipes, etc.; fuel system parts such as fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel pipes, oil strainers, lock nuts, sealing materials, etc.; structural parts such as mount brackets, torque rods, cylinder head covers, etc.; drive system parts such as bearing retainers, gear tensioners, headlamp actuator gears, HVAC gears, sliding door rollers, clutch peripheral parts, etc.; brake system parts such as air brake tubes, etc.; in-vehicle electrical parts such as wire harness connectors, motor parts, sensors, ABS bobbins, combination switches, in-vehicle switches, electronic control unit (ECU) boxes, etc. inside the engine room; interior and exterior parts such as sliding door dampers, door mirror stays, door mirror brackets, inner mirror stays, roof rails, engine mount brackets, air cleaner inlet pipes, door checkers, plastic chains, emblems, clips, breaker covers, cup holders, airbags, fenders, spoilers, radiator supports, radiator grilles, louvers, air scoops, hood bulges, back doors, fuel sender modules, floor mats, instrument panels, dashboards, dash insulators, dam rubbers, weather strips, etc., and tires, etc.

[0088] (3) Various products in the household appliance field: For example, various electrical products such as TVs, various recorders such as Blu-ray recorders and HDD recorders, projectors, game consoles, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, FAX machines, copiers, telephones, door phones, rice cookers, microwave ovens, oven ranges, refrigerators, dishwashers, dish dryers, IH cooking heaters, hot plates, vacuum cleaners, washing machines, chargers, sewing machines, irons, dryers, electric bicycles, air purifiers, water purifiers, electric toothbrushes, lighting fixtures, air conditioners, outdoor units of air conditioners, dehumidifiers, humidifiers, etc. Sealing materials, adhesives, adhesives, packings, O-rings, belts, soundproofing materials, etc.

[0089] In addition, this polymer can also be used as a modifier for improving properties such as the toughness and impact resistance of thermoplastic resins. Examples of the thermoplastic resin in which this polymer is blended as a modifier include polypropylene, polyethylene, polystyrene, polycarbonate, polyester, polyarylene, polyarylene ether, polyarylene sulfide, polyamide, polyimide, ABS resin, etc.

Examples

[0090] Hereinafter, specific explanations will be given based on examples, but the present invention is not limited to these examples. In addition, "parts" and "%" in the examples and comparative examples are based on mass unless otherwise specified.

[0091] 1. Physical property measurement method The measurement methods for various physical property values of the polymer are as follows. [Vinyl bond content]: Measured using a polymer before hydrogenation with a 500 MHz apparatus 1 Calculated from the H-NMR spectrum. [1st peak weight average molecular weight]: Determined in terms of polystyrene from the retention time of the peak with the longest retention time in the GPC curve obtained using gel permeation chromatography (GPC) (HLC-8120GPC (product name, manufactured by Tosoh Corporation)). (GPC conditions) Columns; two columns of product name "GMHXL" (manufactured by Tosoh Corporation) Column temperature; 40 °C Mobile phase; tetrahydrofuran Flow rate; 1.0 ml / min Sample concentration; 10 mg / 20 ml [Total weight average molecular weight]: Determined in terms of polystyrene from the GPC curve obtained using GPC (HLC-8120GPC (product name (manufactured by Tosoh Corporation))). [Coupling ratio]: Calculated from the peak area ratio of the GPC curve obtained using GPC (HLC-8120GPC (product name (manufactured by Tosoh Corporation))). [Hydrogenation ratio]: Measured with a 100 MHz apparatus using ethylene tetrachloride as a solvent 1 Calculated from the 1H-NMR spectrum.

[0092] 2. Production of polymer [Example 1]: Production of polymer (A-1) Into a nitrogen-substituted reaction vessel, 800 parts of degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, 0.14 part of piperidine, and 0.14 part of n-butyllithium were charged, and 30 parts of 1,3-butadiene was added at a polymerization start temperature of 70 °C, followed by temperature-raising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20 °C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-raising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and further temperature-raising polymerization was carried out. The block polymer thus obtained contained a structural unit derived from 1,3-butadiene and had a polymer block A with a vinyl bond content of 15 mol% and a polymer block B with a vinyl bond content of 75 mol% containing a structural unit derived from 1,3-butadiene. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 300,000, and the coupling ratio was 75%. Subsequently, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxychloride were added to the reaction vessel and stirred. The hydrogenation reaction was initiated at a hydrogen gas supply pressure of 0.7 MPa - Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred and added into water. The solvent was removed by steam distillation to obtain a block polymer with a hydrogenation rate of 98% for the conjugated diene moiety (this is designated as block polymer (A-1)). Various physical property values, etc. of the obtained block polymer (A-1) are shown in Table 1.

[0093] [Example 2]: Production of Polymer (A-2) By applying the same formulation as that for polymer (A-1) except that the hydrogen supply amount in the hydrogenation reaction was reduced, a block polymer with a hydrogenation rate of 90% for the conjugated diene moiety (this is designated as block polymer (A-2)) was obtained. Various physical property values, etc. of the obtained block polymer (A-2) are shown in Table 1.

[0094] [Example 3] Production of Polymer (A-3) An 800-part amount of degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, 0.07 part of piperidine, and 0.09 part of n-butyllithium were charged into a reaction vessel purged with nitrogen. 30 parts of 1,3-butadiene was added at a polymerization initiation temperature of 70°C, and temperature-rising polymerization was carried out. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-rising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.06 part of methyldichlorosilane was added, and further temperature-rising polymerization was carried out. The block polymer thus obtained contained structural units derived from 1,3-butadiene, and had a polymer block A with a vinyl bond content of 15 mol% and a polymer block B with a vinyl bond content of 75 mol% that contained structural units derived from 1,3-butadiene. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 180,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Thereafter, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxy chloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred and added to water to remove the solvent by steam distillation, thereby obtaining a block polymer with a hydrogenation rate of 98% in the conjugated diene moiety (this is designated as block polymer (A-3)). Various physical property values, etc. of the obtained block polymer (A-3) are shown in Table 1.

[0095] [Example 4]: Production of Polymer (A-4) An 800-part amount of degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, 0.14 part of piperidine, and 0.14 part of n-butyllithium were charged into a nitrogen-substituted reaction vessel, and 30 parts of 1,3-butadiene was added at a polymerization start temperature of 70°C to conduct temperature-rising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 50 parts of 1,3-butadiene, 20 parts of styrene, and 20 parts of tetrahydrofuran were added, and further temperature-rising polymerization was conducted. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and further temperature-rising polymerization was conducted. The block polymer thus obtained was a block polymer having a polymer block A containing structural units derived from 1,3-butadiene and having a vinyl bond content of 15 mol%, and a polymer block B containing structural units derived from 1,3-butadiene and styrene and having a vinyl bond content of 75%. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Subsequently, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxy chloride were added to the reaction vessel and stirred. The hydrogenation reaction was initiated at a hydrogen gas supply pressure of 0.7 MPa - Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining a block polymer with a hydrogenation rate of 98% in the conjugated diene portion (this is designated as block polymer (A-4)). Various physical property values, etc. of the obtained block polymer (A-4) are shown in Table 1.

[0096] [Example 5]: Production of Polymer (A-5) 800 parts of degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, 0.25 part of N-(tert-butyldimethylsilyl)piperazine, and 0.14 part of n-butyllithium were charged into a nitrogen-substituted reaction vessel, and 30 parts of 1,3-butadiene was added at a polymerization initiation temperature of 70°C to conduct temperature-rising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-rising polymerization was conducted. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and further temperature-rising polymerization was conducted. The block polymer thus obtained contained a structural unit derived from 1,3-butadiene and had a polymer block A with a vinyl bond content of 15 mol% and a polymer block B with a vinyl bond content of 75 mol% that contained a structural unit derived from 1,3-butadiene. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Subsequently, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxy chloride were added to the reaction vessel and stirred. The hydrogenation reaction was initiated at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred and added into water to remove the solvent by steam distillation, thereby obtaining a block polymer with a hydrogenation rate of 98% in the conjugated diene portion (this is designated as block polymer (A-5)). Various physical property values, etc. of the obtained block polymer (A-5) are shown in Table 1.

[0097] [Example 6]: Production Example of Polymer (A-6)> An 800-part degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, 0.14 part of piperidine, and 0.14 part of n-butyllithium were charged into a nitrogen-substituted reaction vessel, and 30 parts of 1,3-butadiene was added at a polymerization start temperature of 70°C for temperature-rising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-rising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.19 part of 1,1’-(1,4-phenylene)bis(N-(3-(triethoxysilyl)propyl)methanimine) was added, and further temperature-rising polymerization was carried out. The block polymer thus obtained was a block polymer having a polymer block A containing structural units derived from 1,3-butadiene with a vinyl bond content of 15 mol% and a polymer block B containing structural units derived from 1,3-butadiene with a vinyl bond content of 75 mol%. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Thereafter, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxy chloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa - Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C and normal pressure, withdrawn from the reaction vessel, and stirred and added into water to remove the solvent by steam distillation, thereby obtaining a block polymer with a hydrogenation rate of 98% in the conjugated diene portion (this is designated as block polymer (A-6)). Various physical property values, etc. of the obtained block polymer (A-6) are shown in Table 1.

[0098] [Example 7]: Production of Polymer (A-7) To 100 parts of block polymer (A-5), 0.5 part of maleic anhydride and 0.25 part of an organic peroxide (t-butyl peroxybenzoate) were mixed with a Henschel mixer for 5 minutes. The obtained mixture was extruded and modified at a cylinder temperature of 200 - 240°C using an extruder with a 30 mm vent to obtain a block polymer (this is designated as block polymer (A-7)). Various physical property values, etc. of the obtained block polymer (A-7) are shown in Table 1.

[0099] [Example 8]: Production of Polymer (A-8) An 800 parts of degassed and dehydrated cyclohexane, 0.03 parts of tetrahydrofuran, 0.14 parts of piperidine, and 0.14 parts of n-butyllithium were charged into a nitrogen-substituted reaction vessel, and 30 parts of 1,3-butadiene was added at a polymerization initiation temperature of 70°C, followed by temperature-rising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-rising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.03 parts of tetrachlorosilane was added, and further temperature-rising polymerization was carried out. The block polymer thus obtained contained a structural unit derived from 1,3-butadiene and had a polymer block A with a vinyl bond content of 15 mol% and a polymer block B with a vinyl bond content of 75 mol% containing a structural unit derived from 1,3-butadiene. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 200,000, and the coupling rate was 40%. Thereafter, 0.05 parts of diethylaluminum chloride and 0.11 parts of bis(cyclopentadienyl)titanium furfuryloxy chloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred and added into water to remove the solvent by steam distillation, thereby obtaining a block polymer (designated as block polymer (A-8)) with a hydrogenation rate of 98% for the conjugated diene portion. Various physical property values, etc. of the obtained block polymer (A-8) are shown in Table 1.

[0100] [Example 9]: Production Example of Polymer (A-9) 800 parts of cyclohexane that had been degassed and dehydrated, 0.03 part of tetrahydrofuran, 0.14 part of piperidine, and 0.14 part of n-butyllithium were charged into a nitrogen-substituted reaction vessel. 30 parts of 1,3-butadiene was added at a polymerization initiation temperature of 70°C, and temperature-raising polymerization was carried out. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 1.5 parts of tetrahydrofuran were added, and further temperature-raising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and further temperature-raising polymerization was carried out. The block polymer thus obtained contained structural units derived from 1,3-butadiene and had a polymer block A with a vinyl bond content of 15 mol% and a polymer block B with a vinyl bond content of 45 mol% that contained structural units derived from 1,3-butadiene. Also, in the obtained block polymer, the 1st peak weight average molecular weight was 100,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Thereafter, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxychloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C at normal pressure, withdrawn from the reaction vessel, and stirred and added to water to remove the solvent by steam distillation, thereby obtaining a block polymer (designated as block polymer (A-9)) with a hydrogenation rate of 98% for the conjugated diene portion. Various physical property values, etc. of the obtained block polymer (A-9) are shown in Table 1.

[0101] [Comparative Production Example 1]: Production of Polymer (A-10) A block polymer (designated as block polymer (A-10)) was obtained by performing the same formulation as that of polymer (A-1) except that piperidine was not added. Various physical property values, etc. of the obtained block polymer (A-10) are shown in Table 1.

[0102] [Comparative Production Example 2]: Production of Polymer (A-11) A block polymer having a hydrogenation rate of 60% in the conjugated diene portion (hereinafter referred to as block polymer (A-11)) was obtained by applying the same formulation as that of polymer (A-1) except for reducing the amount of hydrogen supplied in the hydrogenation reaction. Various physical property values of the obtained block polymer (A-11) are shown in Table 1.

[0103] [Comparative Production Example 3]: Production of Block Polymer (A-12) 800 parts of degassed and dehydrated cyclohexane, 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium were charged into a nitrogen-substituted reaction vessel, and 30 parts of styrene was added at a polymerization start temperature of 70°C, followed by temperature-rising polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, 70 parts of 1,3-butadiene and 16 parts of tetrahydrofuran were added, and further temperature-rising polymerization was carried out. After the polymerization conversion rate reached 99% or more, 0.06 part of methyldichlorosilane was added, and further temperature-rising polymerization was carried out. The block polymer thus obtained did not contain polymer block A, and had a polymer block C composed of structural units derived from styrene and a polymer block B containing structural units derived from 1,3-butadiene and having a vinyl bond content of 75 mol%. In addition, in the obtained block polymer, the 1st peak weight average molecular weight was 180,000, the total weight average molecular weight was 300,000, and the coupling rate was 75%. Thereafter, 0.05 part of diethylaluminum chloride and 0.11 part of bis(cyclopentadienyl)titanium furfuryloxychloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C. After 3.0 hours, the reaction solution was brought to 60°C and normal pressure, withdrawn from the reaction vessel, and stirred and added into water to remove the solvent by steam distillation, thereby obtaining a block polymer having a hydrogenation rate of 98% in the conjugated diene portion (hereinafter referred to as block polymer (A-12)). Various physical property values of the obtained block polymer (A-12) are shown in Table 1.

[0104] [Comparative Production Example 4]: Production of Block Polymer (A-13) To 100 parts of block polymer (A-12), 0.5 part of maleic anhydride and 0.25 part of organic peroxide (t-butyl peroxybenzoate) were mixed in a Henschel mixer for 5 minutes. The resulting mixture was extruded and modified at a cylinder temperature of 200 to 240 °C using an extruder with a 30 mm vent to obtain a block polymer (designated as block polymer (A-13)). Various physical property values of the obtained block polymer (A-13) are shown in Table 1.

[0105] 3. Evaluation of Adhesive Performance

[0106] [Manufacture of Adhesive Film] Using polypropylene (manufactured by Prime Polymer Co., Ltd., J715M) as the base material layer, and using the final product obtained in Example 1 (a mixture of a multi-branched block polymer (A-1) and the unreacted block polymer that was not consumed in the coupling reaction) in the adhesive layer, polypropylene and the above final product were co-extrusion molded (extrusion temperature: 200 to 230 °C, cooling roll: about 50 °C) by the T-die method to form an adhesive film in which a base material layer with a thickness of 40 μm and an adhesive layer with a thickness of 12 μm were laminated and integrated. This adhesive film was wound around a paper core with an inner diameter of 3 inches to obtain a film roll.

[0107] Similarly, using the final products obtained in Examples 2 to 9 and Comparative Production Examples 1 to 4 respectively, adhesive films were formed in the same manner as in Example 1, wound around a paper core with an inner diameter of 3 inches, and film rolls were obtained.

[0108] For each of the obtained adhesive films, the following items (1) to (5) were evaluated. (1) Peel Strength Each adhesive film of the examples and comparative examples was placed on a SUS plate (SUS mirror finish plate) whose surface was polished to a surface roughness of 0.5 to 1.0 μm. In an environment of room temperature 23 °C and relative humidity 50%, using a tabletop laminator, at a pressure of 5.9×10 5They were each pasted at a speed of 30 mm / min. After leaving them for 30 minutes in this environment, in accordance with the method of JIS Z 0237:2009, the 180-degree peel strength of these films (25 mm width) was measured at a speed of 300 mm / min, and this was taken as the initial peel strength. From the obtained initial peel strength, the peel strength was judged according to the following four criteria of A to D. A: 0.30 N / 10 mm or more, and the peel strength is extremely good. B: 0.15 N / 10 mm or more and less than 0.30 N / 10 mm, and the peel strength is good. C: 0.05 N / 10 mm or more and less than 0.15 N / 10 mm, and the peel strength is at an acceptable level. D: Less than 0.05 N / 10 mm, and the peel strength is poor.

[0109] (2) Low adhesive creep Each of the adhesive films of the examples and comparative examples was pasted on the surface of a plate similar to the SUS plate used for the peel strength evaluation in (1) above, in an environment of room temperature 23°C and relative humidity 50%, using a tabletop laminator, at a pressure of 5.9×10 5 Pa and at a speed of 30 mm / min. Next, each adhesive film was left at 60°C for 30 minutes and left at 60°C for 1 week, and in accordance with the method of JIS Z 0237, the 180-degree peel strength of these films (25 mm width) was measured at a speed of 300 mm / min, and these were taken as the initial peel strength and the peel strength over time, respectively. The change ratio (adhesive creep ratio) of the peel strength over time from the initial peel strength was calculated by the following formula (a). Change ratio (adhesive creep ratio) = (Peel strength over time / Initial peel strength) …(a) From the obtained change ratio (adhesive creep ratio), the advancement of adhesiveness was judged according to the following four criteria of A to D. A: The adhesive creep ratio is in the range of 1.2 or less, and the low adhesive creep is extremely good. B: The adhesive creep ratio exceeds 1.2 and is in the range of 1.6 or less, and the low adhesive creep is good. C: The adhesive creep ratio exceeds 1.6 and is in the range of 2.0, and the adhesive creep is at an acceptable level. D: The sticking progress ratio exceeds 2.0, and the low sticking progress property is poor.

[0110] (3) Developability Each pressure-sensitive adhesive film of the examples and comparative examples was attached to a polypropylene film under the environment of room temperature 23°C and relative humidity 50% using a tabletop laminator at a pressure of 5.9×10 5 Pa and a speed of 30 m / min. Then, after leaving it at 60°C for 60 minutes, in accordance with the method of JIS Z0237, the 180-degree peel strength of the pressure-sensitive adhesive film (25 mm width) was measured at a speed of 15 m / min, and this was taken as the developing force. From the obtained developing force, the developability was determined according to the following four criteria of A to D. A: Less than 0.05 N / 10 mm, and the developability is extremely good. B: 0.05 N / 10 mm or more and less than 0.10 N / 10 mm, and the developability is good. C: 0.10 N / 10 mm or more and less than 0.20 N / 10 mm, and the developability is at an acceptable level. D: 0.20 N / 10 mm or more, and there is concern about the adverse effect on the rewinding from the film roll, and the developability is poor.

[0111] (4) Adhesive residue In the evaluation of the low sticking progress property in (3) above, after evaluating the peel strength over time, the surface of the SUS plate was visually observed to confirm the presence or absence of residues of the adhesive layer. From the obtained presence or absence of residues, the adhesive residue was determined according to the following two criteria of A and B. A: There is no residue, and the adhesive residue is good. B: Residues are observed, the contaminability to polar adherends is high, and the adhesive residue is poor.

[0112] (5) Oil resistance After each pressure-sensitive adhesive film was immersed in oleic acid and left at room temperature (23°C) for 1 day, the pressure-sensitive adhesive film was taken out and its appearance was confirmed. From the appearance, the oil resistance was determined according to the following three criteria of A to C. A: There is no change in the appearance of the adhesive layer, and the oil resistance is good. B: Wrinkles are observed on the surface of the adhesive layer, and the oil resistance is at an acceptable level. C: Part of the adhesive layer is dissolved, there is concern about the adverse effect on adhesiveness due to oil adhesion, and the oil resistance is poor.

[0113]

Table 1

[0114] In Table 1, the abbreviations of the monomer, starting-end modifier, coupling agent, and post-modifier represent the following compounds. · BD: 1,3-butadiene · ST: Styrene · R-1: Piperidine · R-2: N-(tert-butyldimethylsilyl)piperazine · C-1: Tetrachlorosilane · C-2: Methyldichlorosilane · C-3: 1,1’-(1,4-phenylene)bis(N-(3-(triethoxysilyl)propyl)methanimine) · D-1: Maleic anhydride

[0115] As shown in the above results, in Examples 1 to 9, all of the peel strength, low adhesion progression, developability, paste residue suppression, and oil resistance were good, and the balance of various properties was achieved. In particular, in Example 6 using a terminal modifier as the coupling agent and Example 7 with post-modification, all evaluations were grade A, indicating particularly excellent performance. In contrast, Comparative Examples 1 to 4 were poor in at least one of the evaluations and were inferior to Examples 1 to 9.

[0116] From the above results, it became clear that the block copolymer of the present disclosure is excellent in initial adhesiveness, low adhesion progression, developability, and oil resistance, and is also less likely to leave paste on the adherend.

Claims

Claim 1. A block polymer, comprising: When the composition ratios (molar ratios) of the structural units represented by the following formula (1), the structural units represented by the following formula (2), the structural units represented by the following formula (3), and the structural units represented by the following formula (4) in the polymer are p, q, r, and s, respectively, the value α represented by the following mathematical formula (i) is 0.75 or more; It has two or more polymer blocks A in which the value β represented by the following mathematical formula (ii) is 0.20 or less; It further has a polymer block B in which the value β is 0.25 or more; A part or all of the terminals of two or more of the polymer blocks A have a functional group F containing at least one element selected from the group consisting of nitrogen, silicon, oxygen, and sulfur, and the functional group F contains at least nitrogen; The polymer block A is disposed at the end of the block polymer; A block polymer having the functional group F at the terminal of the block polymer. α = (p + (0.5 × r)) / (p + q + (0.5 × r) + s) … (i) β = (p + q) / (p + q + (0.5 × r) + s) … (ii) 【Chemical Formula 1】

2. The block polymer according to claim 1, having a structure in which two or more polymer chains having the polymer block A are bonded to a partial structure E derived from a coupling agent.

3. The block polymer according to claim 2, having a structure in which four or more polymer chains having the polymer block A are bonded to the partial structure E.

4. The block polymer according to claim 2 or 3, wherein the coupling agent has a functional group containing nitrogen.

5. The block polymer according to any one of claims 1 to 4, having at least one selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and an imide group as the functional group F.

6. The block polymer according to any one of claims 1 to 5, which is modified with maleic anhydride.

7. The block polymer according to any one of claims 1 to 6, wherein the polymer block B has a structural unit derived from a conjugated diene compound and a structural unit derived from an aromatic vinyl compound.

8. A polymer mixture containing the block polymer according to any one of claims 1 to 7, And a block polymer having one polymer block A, further having a polymer block B in which the value β is 0.25 or more, and the value α is 0.75 or more.

9. An adhesive obtained by using the block polymer according to any one of claims 1 to 7 or the polymer mixture according to claim 8.

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