TW202104320A - Tackifying composition - Google Patents

Abstract

This tackifying composition contains, with respect to 100 parts by mass of a block copolymer or a hydrogenated product thereof, at least one selected from 1-1000 parts by mass of tackifying resins and 1-1000 parts by mass of plasticizing agents. The block copolymer includes a polymeric block (A) and a polymeric block (B), wherein the polymeric block (B) has a structural unit that is derived from a conjugated diene compound and that includes, in a main chain, at least one alicyclic backbone (X) represented by formula (X).

Description

Adhesive composition

The present invention relates to an adhesive composition containing a block copolymer or its hydrogenated product.

Among the block copolymers having polymer blocks containing structural units derived from aromatic vinyl compounds, and polymer blocks containing structural units derived from conjugated diene compounds, and their hydrogenated products are known Vibration damping person, and can be used as a vibration damping material. In addition, the above-mentioned block copolymers and their hydrogenated products are considered to have physical properties such as sound insulation, heat resistance, impact resistance, and adhesive properties in addition to vibration damping properties, and can be used in various applications. . For example, a hydrogenated block copolymer of a styrene-based compound and a conjugated diene compound such as isoprene or butadiene has been disclosed for the purpose of improving vibration resistance, flexibility, heat resistance, tensile strength, and impact resistance. It is excellent in mechanical properties such as properties, and the peak temperature of tanδ and the vinyl bond amount are specified (for example, refer to Patent Documents 1 to 4).

Among the above-mentioned block copolymers, those having a long open time and good adhesiveness are known to be used as adhesives for surface protection films such as diapers and non-woven fabrics, and surface protective films for electrical and electronic parts (such as , Refer to Patent Document 5). In addition, among the above-mentioned block copolymers, those exhibiting vibration damping properties and adhesive properties are known to be used as sealants in, for example, the automotive and construction fields (for example, refer to Patent Document 6). [Prior Technical Literature] [Patent Literature]

Patent Document 1 　 JP 2002-284830 A Patent Document 2 "International Publication No. 2000/015680 Patent Document 3 　 JP 2006-117879 A Patent Document 4 　 JP 2010-053319 A Patent Document 5" International Publication No. 2002/040611 Patent Document 6 ``International Publication No. 2015/087954

[The problem to be solved by the invention]

On the other hand, sometimes the adhered body joined through the adhesive may peel off due to vibration, and the performance of the adhesive is required to improve. In addition, as the temperature rises, the adhesive strength tends to decrease, and it is desirable to maintain the adhesive strength even at high temperatures. Therefore, it is desired that it does not easily peel from the adherend and maintains the adhesive force even at high temperatures. In the adhesive composition, there is still room for improvement for both vibration damping properties and adhesive properties. Therefore, the present invention provides an adhesive composition that has vibration damping properties and is not easy to peel off even at high temperatures. [Means used to solve the problem]

As a result of intensive research in order to solve the above-mentioned problem, the present inventors considered the following invention and found that the problem can be solved. That is, the present invention is as follows.

An adhesive composition containing at least 1 selected from 1 to 1000 parts by mass of adhesion-imparting resin and 1 to 1000 parts by mass of plasticizer relative to 100 parts by mass of the following block copolymer or its hydrogenated product Kind. The aforementioned block copolymer contains a polymer block (A) and a polymer block (B). The polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula in the main chain: (X) One or more structural units of alicyclic skeleton (X) shown in (X).

(上述式(X)中，R¹ ~R³ 各自獨立地表示氫原子或碳數1~11的烴基，複數個R¹ ~R³ 各自可相同或不同。) [發明效果]

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different.) [Effects of the invention]

According to the present invention, it is possible to provide an adhesive composition that has vibration damping properties and is not easily peeled off even at high temperatures.

[Forms used to implement the invention]

≪Adhesive composition≫ The adhesive composition of the present invention is characterized by containing an adhesion-imparting resin selected from 1 to 1000 parts by mass and 1 to 1000 parts by mass of plasticizing resin relative to 100 parts by mass of the following block copolymer or its hydrogenated product At least one of the agents. The aforementioned block copolymer contains a polymer block (A) and a polymer block (B). The polymer block (B) is a structural unit derived from a conjugated diene compound and has a main chain containing the aforementioned formula (X) One or more structural units of alicyclic skeleton (X) shown in (X). The components contained in the adhesive composition are described below.

[Block copolymer or its hydrogenated product] In the embodiment of the present invention (hereinafter, sometimes referred to as "this embodiment"), the block copolymer or its hydrogenated product is used to form an adhesive composition that has vibration damping properties and is not easy to peel off even at high temperatures. Essential ingredients of things. [Polymer block (A)] From the viewpoint of vibration damping properties and mechanical properties, the polymer block (A) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer. The polymer block (A) preferably contains more than 70 mol% of the structural unit derived from the aromatic vinyl compound in the polymer block (A) (hereinafter, sometimes referred to as "aromatic vinyl compound unit"). ") From the viewpoint of mechanical properties, it is more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably substantially 100 mol%.

Examples of the above-mentioned aromatic vinyl compounds include: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6- Dimethylstyrene, 2,4-Dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β -Methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2 ,6-Dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene Methyl styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro- M-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorobenzene Ethylene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-di Chlorostyrene, o-tertiary butyl styrene, m-tertiary butyl styrene, p-tertiary butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o Chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted by silyl groups , Indene, vinyl naphthalene, N-vinyl carbazole, etc. One kind of these aromatic vinyl compounds may be used alone, or two or more kinds may be used. Among them, from the viewpoint of the balance of production cost and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

烯、二戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃等之群組中的至少1種。聚合物嵌段(A)含有該其他不飽和單體單元之情形的結合形態無特別限制，可為隨機、錐狀之任一者。As long as the purpose and effects of the present invention are not hindered, the polymer block (A) may also contain structural units derived from other unsaturated monomers other than aromatic vinyl compounds (hereinafter, sometimes referred to as "other unsaturated monomers"Unit"), but in the polymer block (A), it is preferably 30 mol% or less, more preferably less than 20 mol%, still more preferably less than 15 mol%, and more preferably less than 10 mol% , And more preferably less than 5 mol%, particularly preferably 0 mol%. Examples of the other unsaturated monomers include those selected from butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, Isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-pair

At least one of the group consisting of ene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, and the like. When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited, and it may be random or tapered.

The block copolymer only needs to have at least one of the aforementioned polymer block (A). In the case where the block copolymer has two or more polymer blocks (A), the polymer blocks (A) may be the same or different. In addition, in this specification, the term "different polymer blocks" means the monomer units constituting the polymer blocks, the weight average molecular weight, the stereoisomerism, and each of the monomer units in the case of having plural monomer units. At least one of the ratio of monomer units and the form of copolymerization (random, gradient, block) is different.

(Weight average molecular weight) The weight average molecular weight (Mw) of the polymer block (A) is not particularly limited, but the weight average molecular weight of at least one polymer block (A) among the polymer blocks (A) possessed by the block copolymer It is preferably 3,000 to 60,000, and more preferably 4,000 to 50,000. Since the block copolymer has at least one polymer block (A) with a weight average molecular weight within the above range, it is beneficial to further improve the vibration damping properties. In addition, the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement.

[Content of polymer block (A)] The content of polymer block (A) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 16% by mass or less , Particularly preferably 14% by mass or less. If it is 50% by mass or less, it has appropriate flexibility and can be a block copolymer or its hydrogenated product that does not decrease the tanδ peak top strength and is excellent in vibration damping properties. In addition, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 6% by mass or more. If it is 1% by mass or more, it can be a block copolymer or its hydrogenated product that has better handling properties such as mechanical properties, moldability, and coating properties in various applications of the adhesive composition. In addition, the content of the polymer block (A) in the block copolymer is ^{a value obtained by 1} H-NMR measurement, and more specifically, a value measured according to the method described in the examples.

[Polymer block (B)] The polymer block (B) constituting the block copolymer is a structural unit derived from a conjugated diene compound, and has an alicyclic skeleton (X) containing one or more types represented by the following formula (X) in the main chain The structural unit (hereinafter, sometimes abbreviated as "alicyclic skeleton-containing unit"). In addition, the polymer block (B) may also contain a structural unit derived from a conjugated diene compound (hereinafter, sometimes simply referred to as "conjugated diene unit") that does not contain an alicyclic skeleton (X). The total of the alicyclic skeleton-containing unit and the conjugated diene unit in the polymer block (B) is preferably 50 mol% or more from the viewpoint of exhibiting excellent vibration damping properties, and more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably substantially 100 mol%. When there are two or more polymer blocks (B) in the block copolymer, the polymer blocks (B) may be the same or different.

In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different. The carbon number of the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 (that is, methyl). In addition, the above-mentioned hydrocarbon group may be a straight chain or a branched chain, and may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), R ¹ to R ^{3 are} particularly preferably each independently a hydrogen atom or a methyl group. In addition, in the case of a hydrogenated block copolymer, the vinyl group in the above formula (X) can be hydrogenated. Therefore, in the meaning of the alicyclic skeleton (X) in the hydride, the skeleton in which the vinyl group in the above formula (X) is hydrogenated is also included.

The polymer block (B) is a structural unit derived from a conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by the method described below using anionic polymerization of a conjugated diene compound. However, depending on the conjugated diene compound used, the main chain of the alicyclic skeleton-containing unit contains at least 1 Kind of alicyclic skeleton (X). With the alicyclic skeleton (X) incorporated into the main chain of the structural unit contained in the polymer block (B), the glass transition temperature rises due to the decrease of molecular motion, and the peak top strength of tanδ near room temperature Improved, can show excellent vibration damping performance.

Examples of the above-mentioned conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2 -Methyl-1,3-octadiene, 1,3,7-octatriene, bacteriochlorene, myrcene and chloroprene, etc. Among them, butadiene, isoprene, or a combination of butadiene and isoprene is preferred.

In the case of using butadiene and isoprene in combination, the blending ratio [isoprene/butadiene] (mass ratio) is not particularly limited, but it is preferably 5/95~95/5, More preferably, it is 10/90~90/10, still more preferably 40/60~70/30, particularly preferably 45/55~65/35. In addition, if the mixing ratio [isoprene/butadiene] is expressed in molar ratio, it is preferably 5/95~95/5, more preferably 10/90~90/10, and still more preferably 40/ 60~70/30, particularly preferably 45/55~55/45.

As a specific example, the alicyclic skeleton (X) that is mainly produced when butadiene, isoprene, or both butadiene and isoprene is used as the conjugated diene compound will be described. When butadiene is used alone as the conjugated diene compound, an alicyclic skeleton (X) having a combination of the following substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) only becomes the alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms at the same time. Therefore, as an example of a preferred aspect of the block copolymer or its hydrogenated product, the polymer block (B) has the following structural units: ^{a resin containing R 1} to R ³ in the main chain and simultaneously being hydrogen atoms Cyclic skeleton (X).

In addition, when isoprene is used alone as the conjugated diene compound, an alicyclic skeleton (X) having two combinations of the following substituents (v) and (vi) is mainly produced. In addition, when butadiene and isoprene are used in combination as a conjugated diene compound, an alicyclic skeleton (X) having six combinations of the following substituents (i) to (vi) is mainly produced. (i): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom (ii): R ¹ = hydrogen atom, R ² = methyl, R ³ = hydrogen atom (iii): R ¹ = hydrogen Atom, R ² = hydrogen atom, R ³ = methyl (iv): R ¹ = methyl, R ² = hydrogen atom, R ³ = hydrogen atom (v): R ¹ = methyl, R ² = methyl, R ³ = hydrogen atom (vi): R ¹ = methyl, R ² = hydrogen atom, R ³ = methyl

In the above formula (X), from the viewpoint that the molecular motion becomes smaller and the vibration damping property is further improved by having a substituent that is a hydrocarbon group, at least one alicyclic ring in the polymer block (B) The formula skeleton (X) is preferably an alicyclic skeleton (X'), ^{and at least one of the above-mentioned R 1} to R ³ is a hydrocarbon group with 1 to 11 carbon atoms. Among them, it is more preferable that the hydrocarbon group in the alicyclic skeleton (X') is a methyl group from the viewpoint of efficiently generating an alicyclic skeleton from a conjugated diene compound, vibration damping properties, and mechanical properties. . In particular, it is more preferable that R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and R ¹ to R ^{3 are} not simultaneously an alicyclic skeleton of a hydrogen atom. That is, the polymer block (B) more preferably has the following structural unit: any one or more of the alicyclic skeletons having a combination of the above-mentioned substituents (ii) to (vi) are contained in the main chain.

(Vinyl bonding amount of polymer block (B)) When the structural unit constituting the polymer block (B) is any one of isoprene units, butadiene units, isoprene and butadiene mixture units, the aforementioned alicyclic skeleton is formed The bonding morphology of isoprene and butadiene other than the bonding morphology of (X) can be 1,2-bonding or 1,4-bonding in the case of butadiene. In the case of diene, it can be 1,2-bonded, 3,4-bonded, or 1,4-bonded.

In the block copolymer and its hydrogenated substances, the content of 3,4-bonded units and 1,2-bonded units in the polymer block (B) (hereinafter, sometimes only referred to as "vinyl-bonded The total amount") is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, still more preferably 66 to 95 mol%, and still more preferably 70 to 95 mol%. As long as it is in the above range, excellent vibration damping properties can be exhibited. In addition, the higher the amount of vinyl bonding, the more it tends to suppress the decrease in the peel strength of the adhesive composition due to the increase in temperature, and the adhesive composition becomes less likely to peel off at high temperatures. Here, the vinyl bond amount is a ^{value calculated by 1} H-NMR measurement according to the method described in the examples. In addition, when the polymer block (B) is composed only of butadiene, the aforementioned "content of 3,4-bonding unit and 1,2-bonding unit" is replaced with "1,2- The content of bonding unit" is applied.

(Alicyclic skeleton (X) content) In the polymer block (B), as long as the structural unit containing the alicyclic skeleton (X) is contained in the main chain, it is easy to suppress the viscosity even at high temperatures due to the effect of exhibiting more excellent vibration damping properties. From the viewpoint of the reduction of the subsequent force, the polymer block (B) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, and still more preferably 1.4 mol%. Ear% or more, more preferably 1.8 mol% or more, still more preferably 4 mol% or more, still more preferably 10 mol% or more, and particularly preferably 13 mol% or more. In addition, the higher the content of the alicyclic skeleton (X), the more likely it is that the peel strength of the adhesive composition is suppressed from decreasing due to temperature rise, and the adhesive composition becomes less likely to peel off at high temperatures. In addition, the upper limit of the content of the alicyclic skeleton (X) in the polymer block (B) is not particularly limited as long as it is within a range that does not impair the effect of the present invention, but from the viewpoint of productivity, it is preferably 40. Mole% or less, 30 mole% or less, 20 mole% or less, or 18 mole% or less. From the viewpoint of further improving the vibration damping properties, the polymer block (B) preferably contains 1 mol% or more of the above-mentioned alicyclic skeleton (X'), and still more preferably 1.3 mol% or more. More preferably, it is 1.6 mol% or more. The upper limit of the content of the alicyclic skeleton (X') is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

More specifically, as the conjugated diene compound, when isoprene is used, when butadiene is used, or when butadiene and isoprene are used in combination, the content of alicyclic skeleton in each case The line is as follows. In the case of using isoprene as the conjugated diene compound, in the polymer block (B), an alicyclic skeleton (X') having a combination of the aforementioned substituents (v) and (vi) exists In the case of more than one type, the total content of them is preferably 1 mol% or more from the viewpoint of exhibiting more excellent vibration damping effects and easily suppressing the decrease in adhesive force even at high temperatures. 1.5 mol% or more. From the viewpoint of obtaining excellent vibration damping effects in a wide temperature range, it is more preferably 2 mol% or more, still more preferably 3 mol% or more, and particularly preferably 4 mol% Ear% or more. In addition, the upper limit of the total content in the case of using isoprene is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In the case of using butadiene as the conjugated diene compound, when the alicyclic skeleton (X) is present in the polymer block (B), its content is determined by the effect of exhibiting more excellent vibration damping properties, From the viewpoint of easily suppressing the decrease in adhesive force even at high temperatures, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and still more preferably 20 mol% Ear% or more, more preferably 25 mol% or more, particularly preferably 30 mol% or more. In addition, the upper limit of the content in the case of using butadiene is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In the case where butadiene and isoprene are used in combination as the conjugated diene compound, the polymer block (B) has the aforementioned substituents (ii), (iii), (v), and (vi) When there is more than one kind of alicyclic skeleton (X') in the combination of, the total content of the same is from the viewpoint of exhibiting a more excellent vibration damping effect and easily suppressing the decrease in adhesive force even at high temperatures , Preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, and still more preferably 13 mol% or more. The upper limit of the total content in the case of using butadiene and isoprene in combination is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X). In addition, in the case where butadiene and isoprene are used in combination as the conjugated diene compound, in the polymer block (B), an alicyclic formula having a combination of the aforementioned substituents (i) to (vi) When there is more than one type of skeleton (X), the total content of them is preferably 1 mol from the viewpoint of exhibiting a more excellent vibration damping effect and easily suppressing the decrease in adhesive force even at high temperatures % Or more, more preferably 5 mol% or more. The upper limit of the total content in the case of using butadiene and isoprene in combination is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In addition, the content of the alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product is ^{determined by the 13} C-NMR measurement of the block copolymer and derived from the polymer block ( The value obtained by the integral value of the alicyclic skeleton (X) in B) is, in more detail, the value measured according to the method described in the examples.

In addition, when the hydrogenation rate of the block copolymer or its hydrogenated product in the polymer block (B) is 0 mol% or more and less than 50 mol%, it can be confirmed that the alicyclic skeleton (X) has been bonded The molar ratio between the vinyl group and the vinyl group bonded to the main chain. For example, in an alicyclic skeleton (X') having a combination of substituents (ii), (iii), (v), and (vi), the alicyclic skeleton (X') has been bonded The chemical shift system of the vinyl terminal carbon atom ((a) of the following chemical formula) in ¹³ C-NMR appears in the vicinity of 107~110 ppm, and the vinyl terminal carbon atom that has been bonded to the main chain (the following chemical formula (b)) ^{The chemical shift in 13} C-NMR is around 110~116ppm. In addition, when the hydrogenation rate is 0-40 mol%, ^{the peak area ratio measured by 13} C-NMR [peak area with chemical shift value of 107 to 110 ppm]/[peak area with chemical shift value of 110 to 116 ppm] usually becomes In the range of 0.01 to 3.00, from the viewpoint of exhibiting more excellent vibration damping properties, the area is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, and even better is 0.01 to 0.50, and even better The line becomes 0.01~0.20.

In addition, for the hydride, ^{almost no peak derived from the carbon atom on the alicyclic skeleton (X) was observed in the 13} C-NMR measurement, but the peak derived from the alicyclic skeleton bonded to the branched alkyl group was observed. The peak of the carbon atom on (X), the branched alkyl group is derived from a ^{vinyl group having a substituent R 3} , and the R ³ is a hydrocarbon group having 1 to 11 carbon atoms. From this, regarding the hydrogenated product, when the hydrogenation rate of the polymer block (B) is 50 to 99 mol%, the above-mentioned alicyclic type bonded to the branched alkyl group ^{derived from the vinyl group having R 3 can also be determined} The molar ratio of the carbon atoms on the skeleton (X) and the carbon atoms on the main chain bonded to the branched alkyl group derived from the vinyl group.

For example, in the alicyclic skeleton (X) having a combination of the substituents (iii) and (vi), the carbon atoms on the alicyclic skeleton (X) bonded to the isoprenyl group (below The chemical shift of the chemical formula (c)) in ¹³ C-NMR appears in the vicinity of 50.0~52.0 ppm, and the carbon atom on the main chain bonded to the isoprenyl group ((d) in the following chemical formula) is at ¹³ The chemical shift system in C-NMR appears around 43.0~45.0ppm. In addition, when the hydrogenation rate is 40 to 99 mol%, ^{the peak area ratio measured by 13} C-NMR [peak area with chemical shift value of 50.0-52.0 ppm]/[peak area with chemical shift value of 43.0-45.0 ppm] Usually it is in the range of 0.01 to 3.00. From the viewpoint of exhibiting more excellent vibration damping properties, the area is preferably in the range of 0.01 to 1.50, more preferably in the range of 0.01 to 1.00, and even more preferably in the range of 0.01 The range of ~0.50, the best system becomes 0.01~0.25. In addition, the above-mentioned peak area ratio can be measured in more detail according to the method described in Examples.

(Weight average molecular weight) The total weight average molecular weight of the polymer block (B) of the block copolymer is preferably 15,000 to 15,000 in the state before hydrogenation from the viewpoints of vibration damping properties and handling properties of the adhesive composition. 800,000, more preferably 50,000~700,000, still more preferably 70,000~600,000, particularly preferably 90,000~500,000, most preferably 130,000~450,000.

烯、二戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃、1,3-環戊二烯、1,3-環己二烯、1,3-環庚二烯、1,3-環辛二烯等之群組的至少1種化合物。 嵌段共聚物只要具有至少1個前述聚合物嵌段(B)即可。在嵌段共聚物具有2個以上的聚合物嵌段(B)之情形中，該等聚合物嵌段(B)可相同亦可不同。(Other structural units) The polymer block (B) may contain structural units derived from other polymerizable monomers other than the aforementioned conjugated diene compound as long as it does not interfere with the purpose and effects of the present invention. In this case, in the polymer block (B), the content of structural units derived from polymerizable monomers other than the conjugated diene compound is preferably less than 50 mol%, more preferably less than 30 mol% , More preferably less than 20 mol%, more preferably less than 10 mol%, particularly preferably 0 mol%. As the other polymerizable monomers, for example, selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tertiary butyl Aromatic vinyl compounds such as styrene, 2,4-dimethylstyrene, N-vinylcarbazole, vinyl naphthalene and vinyl anthracene, as well as methyl methacrylate, methyl vinyl ether, β-pine Ene, 8,9-pair

Ene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3 -At least one compound of the group of cyclooctadiene and the like. The block copolymer only needs to have at least one of the aforementioned polymer block (B). In the case where the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.

[Production method] (Block copolymer) As a method of producing a block copolymer, for example, one or more conjugated diene compounds are used as monomers and polymerized by an anionic polymerization method, thereby forming an alicyclic skeleton (X) containing the aforementioned alicyclic skeleton in the main chain. In the polymer block (B) of the structural unit, the monomers of the polymer block (A) are added, and the monomers and conjugated diene compounds of the polymer block (A) are further added successively according to the needs, so that the Obtain a block copolymer. The method for generating an alicyclic skeleton by the above-mentioned anionic polymerization method can use a well-known technique (for example, refer to the specification of US Patent No. 3,966,691). The alicyclic skeleton is formed at the end of the polymer by depletion of monomers, and by further adding monomers to it successively, the polymerization can be restarted from the alicyclic skeleton. Therefore, the presence or absence and content of the alicyclic skeleton can be adjusted according to the successive addition time of the monomers, the polymerization temperature, or the type and amount of the catalyst, the combination of the monomer and the catalyst, and the like. In addition, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and a Lewis base as required can be used.

In the above method, the organolithium compound that can be used as a polymerization initiator for anionic polymerization includes, for example, methyl lithium, ethyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, and pentyl lithium. Base lithium and so on. In addition, examples of dilithium compounds that can be used as a polymerization initiator include naphthalene dilithium, dilithium hexylbenzene, and the like. As a coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate, etc. are mentioned, for example. The usage amount of these polymerization initiators and coupling agents can be appropriately determined according to the desired weight average molecular weight of the block copolymer and its hydrogenated product. Generally speaking, the initiator such as alkyl lithium compound and dilithium compound is preferably based on the total mass of the monomers such as the polymer block (A) and the conjugated diene compound used in the polymerization per 100 mass The parts are used in a ratio of 0.01 to 0.2 parts by mass. When a coupling agent is used, it is preferably used in a ratio of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the aforementioned monomers.

The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. Examples include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatics such as benzene, toluene, and xylene. Hydrocarbon etc. In addition, the polymerization reaction is usually carried out at a temperature of 0 to 100°C, preferably 10 to 70°C, for 0.5 to 50 hours, preferably 1 to 30 hours.

啉等胺類；三級丁醇鈉、三級戊醇鈉或異戊醇鈉等脂肪族醇的鈉或鉀鹽、或者二烷基環己醇鈉、例如如薄荷醇鈉(sodium mentholate)般的脂環式醇的鈉或鉀鹽等金屬鹽等。此等路易斯鹼可單獨使用一種或組合二種以上而使用。In addition, by adding a Lewis base as a co-catalyst during the polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B) can be increased, and the content of 3,4- The content of bonding and 1,2-bonding. Usable Lewis bases include, for example, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-bis(2-tetrahydrofuryl)propane (DTHFP); ethylene glycol dimethyl ether, diethylene glycol Dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and other glycol ethers; triethylamine, N,N,N',N'-tetramethylene diamine, N,N, N',N'-tetramethylethylenediamine (TMEDA), N-methyl

Amines such as morpholines; sodium or potassium salts of aliphatic alcohols such as sodium tertiary butoxide, sodium tertiary pentanoxide, or sodium isoamyloxide, or sodium dialkylcyclohexanoxide, such as sodium mentholate Metal salts such as sodium or potassium salt of the alicyclic alcohol. These Lewis bases can be used individually by 1 type or in combination of 2 or more types.

The amount of Lewis base added depends on how much the content of the alicyclic skeleton (X) is controlled, and the polymer block (B) specifically contains a structure derived from isoprene and/or butadiene In the case of the unit, it is determined how much the vinyl bonding amount of the isoprene unit and/or butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of Lewis base added is not strictly limited, but it is usually 0.1 to 1,000 moles per 1 gram atom of the lithium contained in the alkyl lithium compound or dilithium compound used as the polymerization initiator. The ears are preferably used in the range of 1-100 mol.

The average feed rate of the conjugated diene compound (hereinafter, sometimes referred to as the "average diene feed rate"), from the viewpoint of increasing the content of the alicyclic skeleton (X), per 1 mole of active end , Preferably 150kg/h or less, more preferably 110kg/h or less, still more preferably 55kg/h or less, 45kg/h or less, 30kg/h or less, or 22kg/h or less. From the viewpoint of improving productivity, the lower limit is per 1 mole of active end, preferably 1 kg/h or more, more preferably 3 kg/h or more, still more preferably 5 kg/h or more, and may also be 7 kg/ h or more, may be 10kg/h or more, or 15kg/h or more.

After polymerization by the above method, active hydrogen compounds such as alcohols, carboxylic acids, and water are added to stop the polymerization reaction, thereby obtaining a block copolymer.

(Hydride) When the block copolymer obtained by the above-mentioned production method is used as a hydrogenated product, a hydrogenation reaction is carried out in the presence of a hydrogenation catalyst in an inert organic solvent. Through the hydrogenation reaction, the carbon-carbon double bond derived from the conjugated diene compound in the polymer block (B) in the block copolymer is hydrogenated to become a hydrogenated product of the block copolymer. For the hydrogenation reaction, the hydrogen pressure can be set to about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, and the reaction temperature is set to about 20 to 250°C, preferably 50 to 180° C., more preferably 70 ~180°C, and the reaction time is usually about 0.1 to 100 hours, preferably 1 to 50 hours. Examples of hydrogenation catalysts include Reich's nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on monomers such as carbon, alumina, and diatomaceous earth; and include transition metal compounds and Ziegler-based catalysts, metallocene-based catalysts, etc., which are combinations of alkyl aluminum compounds, alkyl lithium compounds, etc.

The hydride obtained in this way can be coagulated by injecting the polymerization reaction liquid into methanol or the like, and then dried under heating or reduced pressure, or it can be mixed with the solvent by pouring the polymerization reaction liquid and steam into hot water. The so-called steam stripping, which is removed by boiling, is obtained by heating or drying under reduced pressure.

Whether to use the above-mentioned block copolymer or hydrogenated compound can be specified according to the desired performance in various applications of the adhesive composition. Similarly, the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) when it is made into a hydrogenated product can be specified in accordance with the performance desired in the various applications of the adhesive composition. . For example, the higher the hydrogenation rate of the hydride, the higher the heat resistance and weather resistance. The hydrogenation rate can be set to, for example, 50 mol% or more and 99 mol% or less, 60 mol% or more and 99 mol% or less, 70 mol% or more and 99 mol% or less, 80 mol% or more, and Below 99 mol%.

Therefore, it can be a block copolymer or its hydrogenated product with a hydrogenation rate of the polymer block (B) of 0 mol% or more (that is, including the case where it is not hydrogenated) and less than 50 mol%, and also It can be a hydrogenated product with a hydrogenation rate of 50-99 mol% of the polymer block (B). In addition, the above-mentioned hydrogenation rate is based on the content of the carbon-carbon double bond in the structural unit derived from the conjugated diene compound and the alicyclic skeleton (X) in the polymer block (B) by ¹ H- after hydrogenation. The value obtained by the NMR measurement is, more specifically, the value measured according to the method described in the examples.

(Combination style of polymer block (A) and polymer block (B)) The block copolymer is not limited as long as the polymer block (A) and the polymer block (B) can be combined. The combination can be linear, branched, radial, or a combination of two or more of these Combine any of the styles. Among them, the combination of the polymer block (A) and the polymer block (B) is preferably linear. As an example, A represents the polymer block (A) and B represents the polymer block. (B) In the case of (B), the diblock copolymer represented by AB, the triblock copolymer represented by ABA or BAB, the tetrablock copolymer represented by ABAB, the five represented by ABABA or BABAB Block copolymers, (AB) nZ type copolymers (Z represents a coupling agent residue, n represents an integer of 3 or more), and the like. Among them, a linear triblock copolymer or a diblock copolymer is preferred. From the viewpoints of flexibility and ease of production, it is preferred to use an A-B-A type triblock copolymer. As an A-B-A type triblock copolymer, specifically, styrene-butadiene/isoprene-styrene copolymer is mentioned. Among them, the adhesive composition is preferably a hydrogenated product containing at least a styrene-hydrogenated butadiene/isoprene-styrene copolymer as a block copolymer.

Herein, in this specification, when the same type of polymer blocks are combined linearly via a difunctional coupling agent or the like, the entire combined polymer blocks are regarded as one polymer block. Accordingly, including the above-mentioned examples, the polymer block that should be strictly labeled as YZY (Z represents the coupling residue), except for the case where it is particularly necessary to distinguish it from the separate polymer block Y, is represented as a whole Is Y. In this specification, since such a polymer block containing a coupling agent residue is considered as described above, for example, a polymer block containing a coupling agent residue and strictly speaking should be marked as ABZBA (Z represents a coupling agent residue) The block copolymer system is labeled ABA and is regarded as an example of a triblock copolymer.

(Content of polymer blocks (A) and (B)) In the block copolymer, as long as it does not interfere with the purpose and effects of the present invention, it may also contain a polymer block composed of other monomers other than the aforementioned polymer blocks (A) and (B), but the aforementioned polymer block The total content of (A) and the aforementioned polymer block (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. As long as the content is 90% by mass or more, it is possible to produce an adhesive composition that is more excellent in damping properties and easily suppresses the decrease in adhesive force even at high temperatures.

(Weight average molecular weight) The weight average molecular weight (Mw) of the block copolymer and its hydrogenated product obtained by gel permeation chromatography in terms of standard polystyrene is preferably 15,000~800,000, more preferably 50,000~700,000, More preferably, it is 60,000~600,000, more preferably 70,000~600,000, particularly preferably 90,000~500,000, and most preferably 130,000~450,000. If the weight average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, the heat resistance becomes high, and if it is 800,000 or less, the handleability of the adhesive composition becomes good.

[tanδ] (Peak top temperature and intensity of tanδ) Tanδ (loss tangent) is the ratio of loss modulus/storage modulus at a frequency of 1 Hz in dynamic viscoelastic measurement. The peak top temperature and strength of tanδ greatly contribute to vibration damping and other physical properties. Here, the peak top intensity of tanδ refers to the value of tanδ when the peak of tanδ becomes the maximum. In addition, the peak top temperature of tanδ refers to the temperature at which the peak of tanδ becomes the maximum.

In this specification, the peak top temperature and strength of the tanδ of the block copolymer or its hydrogenated product are made by pressing the block copolymer or its hydrogenated product at a temperature of 230°C and a pressure of 10 MPa for 3 minutes to produce a unit with a thickness of 1.0 mm. For the layered piece, the single-layered piece was cut into a disc shape, and this was used as a test piece for measurement. The measurement conditions are based on JIS K 7244-10 (2005), with a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 100°C, and a heating rate of 3°C/min. In addition, the peak top temperature and tanδ intensity of the block copolymer or its hydrogenated product are, more specifically, values measured according to the method described in the examples.

The block copolymer or its hydrogenated product has a peak top intensity of 1.0 or more that can be tan δ by the above measurement. Among the higher ones, it is 1.5 or more, and some of them are 1.9 or more. The higher the peak top strength of tanδ, the better the physical properties such as vibration damping properties at temperature. If it is 1.0 or more, sufficient vibration damping properties can be obtained under actual use environments. In addition, the peak top temperature of the tanδ of the block copolymer or its hydrogenated product is preferably -50°C or higher, more preferably -40°C or higher, still more preferably -30°C or higher, and still more preferably -25°C or higher. It can be above 0°C. In addition, the upper limit of the peak top temperature of tanδ may be a range that does not impair the effects of the present invention, and may be 50°C or lower, 40°C or lower, or 35°C or lower. The range of the peak top temperature of tanδ is, for example, preferably -50 to 50°C, more preferably -40 to 40°C, still more preferably -30 to 30°C, and still more preferably -25 to 25°C. As long as the peak top temperature of tanδ is -50°C or higher, sufficient vibration damping properties can be obtained in an actual use environment, and if it is 50°C or lower, the adhesive composition can exhibit the desired adhesiveness.

(tanδ becomes the maximum width of the temperature range above 1.0) In addition, the block copolymer or its hydrogenated product has a continuous temperature range in which the tanδ at -70 to 100°C measured by the above measurement conditions becomes 1.0 or more. The maximum width of the temperature range is preferably 12°C or more, and more It is preferably 13°C or higher, more preferably 15°C or higher, and still more preferably 17°C or higher. As mentioned above, in the structural unit of the polymer block (B), the aforementioned alicyclic skeleton (X) is incorporated into the main chain, and the molecular motion becomes smaller due to the higher vinyl bonding amount, so the glass transfer The temperature will rise, and the glass transition will be gentler with respect to the temperature change. Thereby, the temperature range in which the tanδ of the block copolymer or its hydrogenated product is 1 or more is widened, and it becomes possible to exhibit vibration damping properties in a wide temperature range. As long as the maximum width of the temperature range in which tanδ becomes 1.0 or more is 12°C or more, and furthermore, 13°C or more, more excellent vibration damping properties can be obtained in an actual use environment. In addition, there is no particular upper limit for the maximum width of the temperature range, but from the viewpoint of productivity, for example, the upper limit may be 35°C, 30°C, or 25°C.

[Adhesive Resin] The adhesive composition may contain an adhesion-imparting resin from the viewpoint of improving handleability and adhesive strength. Examples of the adhesion-imparting resin include: benzofuran resins such as coumarone-indene resin; p-tertiary butylphenol-acetylene resin, phenol-formaldehyde resin, terpene-phenol resin, polyterpene resin, xylene- Phenolic resins and terpene resins such as formaldehyde resins; petroleum resins such as aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, and modified alicyclic petroleum resins; Rosin ester represented by neopentyl erythritol ester of rosin and glyceryl ester of rosin, hydrogenated rosin, methyl ester of hydrogenated rosin, neopentyl erythritol ester of polymerized rosin, hydrogenated rosin ester, high melting point ester resin, polymerized rosin, Rosin-based resins such as hardened rosin and special rosin esters. Among them, as the adhesion-imparting resin, an alicyclic saturated hydrocarbon-based resin can be suitably used. Examples of the alicyclic saturated hydrocarbon-based resin include hydrogenated aromatic petroleum resins, and commercial products such as the "ALCON" series manufactured by Arakawa Chemical Industry Co., Ltd. can also be used. These adhesion-imparting resins may be used alone or in combination of two or more kinds. In addition, from the viewpoints of reducing the residual glue of the resulting adhesive composition and improving the heat resistance and weather resistance, and in the case where the preferred use is to avoid the coloration of the sealant, etc., it is preferable to use a hydrogenated adhesive Give resin. The softening point of the adhesive imparting resin is preferably 85 to 160°C, more preferably 90 to 150°C, and still more preferably 95 to 145°C. As long as the softening point of the adhesion-imparting resin is 85°C or higher, it becomes easy to suppress the decrease in adhesive retention at high temperature (about 60°C), and as long as it is 160°C or lower, the handling properties of the adhesive composition are good.

[Plasticizer] The adhesive composition may contain a plasticizer from the viewpoint of exhibiting flexibility and making it easy to impart adhesiveness. Examples of plasticizers include: paraffin-based, naphthenic-based, and aromatic-based processing oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; minerals Oil; liquid co-oligomer of ethylene and α-olefin; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisoprene, liquid polyisoprene/ Liquid polydienes such as butadiene copolymers, liquid styrene/butadiene copolymers, and liquid styrene/isoprene copolymers and their hydrogenated products. Among them, from the viewpoint of compatibility with block copolymers and their hydrogenated products, paraffin-based processing oils are preferred; liquid co-oligomers of ethylene and α-olefins; liquid paraffins; low molecular weight polyisobutylene; And these hydrides are more preferably hydrides of paraffin-based processing oils. These plasticizers may be used alone, or two or more types may be used in combination.

[Filler] In the adhesive composition, fillers can be included in accordance with the characteristics required in various applications. Examples of fillers include talc, mica, calcium silicate, glass, glass flakes, glass beads, glass hollow spheres, glass fibers, calcium carbonate, magnesium carbonate, zinc carbonate, basic magnesium carbonate, aluminum hydroxide, Magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, silica alumina, diatomaceous earth, wollastonite, zeolite, diaspore, aluminum Sodium silicate, magnesium silicate, graphene, barium carbonate, silicon nitride, aluminum nitride, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), magnesium silicate ( Othepite), aluminum borate, calcium sulfate, magnesium sulfate, aluminum oxide, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, naphthalene Rice carbon tube, graphite, carbon fiber, activated carbon, carbon hollow sphere, calcium titanate, lead zirconate titanate, silicon carbide and other inorganic fillers; wood flour, starch and other organic fillers; organic pigments, etc. These fillers may be used alone, or two or more of them may be used in combination.

[content] In this embodiment, the adhesive composition contains at least one selected from 1 to 1000 parts by mass of an adhesion-imparting resin and 1 to 1000 parts by mass of a plasticizer with respect to 100 parts by mass of the block copolymer or its hydrogenated product. The adhesion-imparting resin and the plasticizer may contain either or both according to the application of the adhesion composition. If the above-mentioned content of the adhesion-imparting resin is less than 1 part by mass, the performance of the adhesion-imparting resin cannot be imparted to the adhesive composition, and if it is more than 1000 parts by mass, the adhesive force at low temperatures may decrease. In addition, if the above-mentioned content of the plasticizer is less than 1 part by mass, the performance of the plasticizer cannot be imparted to the adhesive composition, and if it is more than 1000 parts by mass, the adhesive strength at high temperatures may decrease.

From the viewpoint of easy maintenance of adhesive force even at high temperatures, the content of the adhesion-imparting resin is preferably 120 to 1000 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product. In addition, from the viewpoints of easily exhibiting good handling properties of the adhesive composition and easily maintaining better adhesive force, the content of the adhesion-imparting resin is better than 100 parts by mass of the block copolymer or its hydrogenated product It is 130 parts by mass or more, more preferably 140 parts by mass or more. On the other hand, from the viewpoint of adhesion at low temperature, the content of the adhesion-imparting resin is more preferably 900 parts by mass or less, and more preferably 700 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product Hereinafter, it is more preferably 400 parts by mass or less.

From the viewpoint of easily imparting flexibility and adhesiveness, the content of the plasticizer is preferably 60 to 1000 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product. In addition, from the viewpoint of excellent handling and flexibility of the adhesive composition, the content of the plasticizer is more preferably 70 parts by mass or more relative to 100 parts by mass of the block copolymer or its hydrogenated product, and even more preferably It is 80 parts by mass or more. On the other hand, from the viewpoint of proper flexibility and adhesion, the content of the plasticizer is more preferably 900 parts by mass or less, and more preferably 700 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product. Parts by mass or less, more preferably 400 parts by mass or less.

In addition, in this embodiment, the content of the filler in the adhesive composition is not particularly limited as long as the effect of the present invention is not impaired, and can be appropriately adjusted according to the application of the adhesive composition. From the viewpoint of appropriately exhibiting the flexibility and vibration damping properties of the adhesive composition, the content of the filler is preferably 10 to 2500 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product. In addition, from the viewpoint of excellent handling and flexibility of the adhesive composition, the content of the filler is more preferably 15 parts by mass or more with respect to 100 parts by mass of the block copolymer or its hydrogenated product, and still more preferably 20 parts by mass or more. On the other hand, from the viewpoint of excellent vibration damping properties and easy maintenance of adhesiveness even at high temperatures, the content of the filler is more preferably 2400 mass parts relative to 100 parts by mass of the block copolymer or its hydrogenated product. Parts or less, more preferably 2200 parts by mass or less.

The total content of the block copolymer or its hydrogenated product in the adhesive composition, at least one selected from adhesion-imparting resins and plasticizers, and fillers is preferably 80% by mass or more, more preferably 85% by mass or more , More preferably 90% by mass or more.

In addition, in this embodiment, the content of each component can be specified in a preferable range according to the application of the adhesive composition. An example of the content corresponding to the application of the adhesive composition is disclosed below, but it is not limited to this. (Surface protection film) When the adhesive composition is used for the adhesive layer in the surface protection film containing the adhesive layer, relative to 100 parts by mass of the block copolymer or its hydrogenated product, the content of the adhesive imparting resin is determined by the appropriate adhesive force and residual From the viewpoint of the balance of less glue, it is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and still more preferably 10 to 70 parts by mass. In the same case, from the viewpoint of the balance between exudation suppression and adhesive force, the content of the plasticizer is preferably 0-100 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product, and more It is preferably 0 to 90 parts by mass, and more preferably 0 to 80 parts by mass.

(Hot melt adhesive) When the adhesive composition is used in a hot melt adhesive, relative to 100 parts by mass of the block copolymer or its hydrogenated product, the content of the adhesive imparting resin varies from the adhesive force at room temperature to high temperature and the adhesive force at low temperature From the viewpoint of the balance of, it is preferably 30 to 1000 parts by mass, more preferably 50 to 700 parts by mass, and still more preferably 100 to 500 parts by mass. In the same situation as above, from the viewpoint of the balance of the adhesive force at low temperature and the holding force at room temperature to high temperature, the content of the plasticizer is preferably relative to 100 parts by mass of the block copolymer or its hydrogenated product 0~1000 parts by mass, more preferably 10~500 parts by mass, still more preferably 25~300 parts by mass.

[additive] The adhesive composition may contain various additives other than the above-mentioned block copolymer and its hydrogenated product, adhesion-imparting resin, plasticizer, and filler within a range that does not impair the effects of the present invention. Examples of additives include cross-linking agents (isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, acridine-based cross-linking agents, amine resins, etc.), heat stabilizers, and light stabilizers. Agent, ultraviolet absorber, infrared absorber, antioxidant, lubricant, coloring agent, antistatic agent, flame retardant, water repellent, water repellent, hydrophilicity imparting agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave Barrier property imparting agent, light transmittance modifier, fluorescent agent, slip property imparting agent, transparency imparting agent, anti-blocking agent, metal inertizer, antibacterial agent, crystal nucleating agent, tortoise Cracking inhibitors, ozone deterioration inhibitors, rodent inhibitors, dispersants, tackifiers, lightfast agents, weathering agents, copper damage inhibitors, reinforcing agents, antifungal agents, macrocyclic molecules (cyclodextrin, calixarene, Cucurbituril (cucurbituril, etc.), olefin resins, and resins other than olefin resins. Examples of olefin resins include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; Single polymer or copolymer of α-olefin; propylene and/or copolymer of ethylene and α-olefin, etc. As the above-mentioned α-olefins, for example, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene and other α-olefins with a carbon number of 20 or less. One or two or more of these can be used. In addition, modified olefin resins in which these olefin resins are modified by maleic acid or the like can also be used. Examples of resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, and nitrile Rubber, butyl rubber, natural rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, Metal ion cross-linked resins of ethylene-(meth)acrylic acid copolymers (ionomers), polystyrene, AS resins, ABS resins and other styrene resins, polyphenylene ether resins, nylon 6, nylon 66 Polyamide resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyurethane resins, polyoxymethylene homopolymers, polyoxymethylene copolymers, etc. Acrylic resins such as aldehyde resins and polymethyl methacrylate resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl chloride-vinyl acetate copolymers, and the like. The above-mentioned additives may be contained within a range that does not impair the effects of the present invention. On the other hand, from the viewpoint of maximizing the effect of the present invention, in the adhesive composition, the content of the additives is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less . As long as the content of the additive is 10% by mass or less, it is considered that it hardly affects the performance of the tanδ strength described later. The total content of the block copolymer or its hydrogenated product in the adhesive composition, at least one selected from adhesion-imparting resins and plasticizers, and fillers is preferably 80% by mass or more, more preferably 85% by mass or more It is more preferably 90% by mass or more, 95% by mass or more, or 98% by mass or more.

[Preparation method of adhesive composition] The preparation method of the adhesive composition is not particularly limited, and for example, it can be prepared using a kneading device. As the kneading device, a method generally used in this field can be used. As long as the ingredients are mixed using a mixer such as a Henschel mixer, V-blender, belt blender, drum blender, cone blender, etc., or after they are mixed, use a single shaft Or a twin-screw extruder, kneader, etc. may be kneaded. The temperature during melt kneading can be appropriately set, but is usually 150 to 300°C, preferably 160 to 250°C. The resulting adhesive composition can be made into an appropriate form depending on the application, usage, etc., for example, it can be in the form of granules, flakes, or pellets. In addition, the adhesive composition can be prepared by dissolving and mixing each component in various organic solvents, and then removing the organic solvent by drying or the like. Examples of organic solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, tertiary butanol, secondary butanol, acetone, and acetone. Aliphatic solvents such as acetone, cyclohexanone, heptane, isopentane, n-hexane, and cyclohexane, aromatic solvents such as benzene, toluene, and ethylbenzene.

≪Physical properties of adhesive composition≫ [tanδ intensity] The above-mentioned block copolymer or its hydrogenated product can exhibit excellent vibration damping properties. Therefore, the adhesive composition containing the block copolymer or its hydrogenated product also has a peak top strength of tanδ of preferably 1.0 or more, more preferably 2.0 or more, and still more preferably 2.6 or more. The peak top temperature of the adhesive composition is preferably -10°C or higher, more preferably 0°C or higher. The upper limit of the peak top temperature of the adhesive composition may be in a range that does not impair the effects of the present invention, and may be 50°C or lower, or 40°C or lower. In addition, the tanδ strength of the adhesive composition at a temperature of 23° C. is preferably 0.15 or more, more preferably 0.30 or more, and still more preferably 0.50 or more. The tanδ strength of the adhesive composition at a temperature of 40°C is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more. The tanδ strength of the adhesive composition at a temperature of 60°C is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more.

[Storage Modulus] In this embodiment, the ratio of the shear storage modulus G'(23°C) at 23°C to the shear storage modulus G'(60°C) [G'(23°C)/G'(60°C)] , Preferably 1.3 or more. In this embodiment, the adhesive composition contains the above-mentioned block copolymer or its hydrogenated product, and the above-mentioned storage modulus ratio [G'(23℃)/G'(60℃)] becomes easy to achieve 1.3 and above. Generally speaking, the adhesive force decreases as the temperature becomes higher, but in this embodiment, as long as the storage modulus ratio [G'(23°C)/G'(60°C)] is 1.3 or more, then The degree of decrease in peel strength from 23°C to 60°C becomes smaller, and it tends to be less likely to peel even at high temperatures. In this embodiment, the ratio of the storage modulus [G'(23°C)/G'(60°C)] is adjusted by adjusting the adhesive composition (the above-mentioned block copolymer or its hydrogenated product, the above-mentioned viscosity Then the resin, the above-mentioned plasticizer, and the above-mentioned filler and the type and content of optional components), etc., can also be 1.5 or more, or even 1.7 or more. In addition, the shear storage modulus, in more detail, is a value measured according to the method described in the examples.

[Peel strength] In this embodiment, the peel strength of the adhesive composition is based on the acrylic resin plate as the adherend. The 180° peel strength measured in accordance with JIS Z 0237 (2009) is preferably 10.0N at a measurement temperature of 23°C. /25mm or more, more preferably 15.0N/25mm or more, even more preferably 20.0N/25.0mm or more, and even more preferably 25.0N/25.0mm or more. In addition, the peel strength under the same conditions is preferably 5.0N/25mm or more at a measurement temperature of 60°C, more preferably 8.0N/25mm or more, even more preferably 11.0N/25mm or more, and even more preferably 12.0N/25mm or more, especially preferably 14.0N/25mm or more. Generally speaking, the adhesive force decreases as the temperature becomes higher. However, in this embodiment, by including the above-mentioned block copolymer or its hydrogenated product and adjusting its content to a preferable range, it becomes It is easy to achieve the above-mentioned adhesion. Furthermore, in this embodiment, the ratio of the peel strength at 60°C to the peel strength at 23°C of the adhesive composition can also be 0.2 or more, even 0.3 or more, or even 0.4 or more. The ratio of the peel strength is adjusted by adjusting the composition of the adhesive composition (the above-mentioned block copolymer or its hydrogenated product, the above-mentioned adhesive resin, the above-mentioned plasticizer, and the above-mentioned filler and optional component types and Content) and so on. In addition, the peel strength, in more detail, is a value measured according to the method described in the examples.

≪Use≫ It can be made into an adhesive containing the above-mentioned adhesive composition. The adhesive can also be used by heating and melting, for example. In addition, for the adhesive, various organic solvents can be used, for example, the solid content concentration may be about 5 to 70% by mass, and the adhesive can be dissolved and used as a solution adhesive. Examples of organic solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, tertiary butanol, secondary butanol, acetone, and acetone. Aliphatic solvents such as acetone, cyclohexanone, heptane, isopentane, n-hexane, and cyclohexane, aromatic solvents such as benzene, toluene, and ethylbenzene. In addition, it can be used as a hot melt adhesive containing an adhesive composition, such as a block copolymer or its hydrogenated product, an adhesion-imparting resin, and an adhesive composition containing a plasticizer as needed. Fusion agent.

[Sealants] It can be made into a sealant containing the above-mentioned adhesive composition. The above-mentioned adhesive composition can be directly used as a sealant, but it can also be cross-linked as needed within a range that does not impair the effect of the present invention. In the case of cross-linking, a cross-linking agent such as a radical generator, sulfur, or a sulfur compound can be used. Furthermore, in the case of using sulfur or a sulfur compound for cross-linking, a vulcanization accelerator can also be used as a cross-linking aid as needed.

基過氧化物、二

基過氧化物、α,α’-雙(三級丁基過氧基)-對二異丙基苯、2,5-二甲基-2,5-二(三級丁基過氧基)己烷、2,5-二甲基-2,5-二(三級丁基過氧基)-己炔-3等二烷基過氧化物；乙醯基過氧化物、丁二酸過氧化物、苯甲醯基過氧化物等二醯基過氧化物；三級丁基過氧基乙酸酯、三級丁基過氧基異丁酸酯、三級丁基過氧基異丙基碳酸酯等過氧化酯、甲基乙基酮過氧化物、環己酮過氧化物等過氧化酮等之有機過氧化物；過氧化氫、過硫酸鹽、金屬氧化物等無機過氧化物、偶氮化合物、一及二硫化物、金屬螯合劑、氧化還原起始劑等。使用此等自由基產生劑之情形，相對於嵌段共聚物或其氫化物100質量份，較佳為在0.01~15質量份，更佳為在0.05~10質量份的範圍內使用。Examples of radical generators include hydroperoxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide. Substances; di-tertiary butyl peroxide, tertiary butyl

Base peroxide, two

Peroxide, α,α'-bis(tertiary butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-bis(tertiary butylperoxy) Dialkyl peroxides such as hexane, 2,5-dimethyl-2,5-di(tertiary butylperoxy)-hexyne-3; Acetyl peroxide, succinic acid peroxide Diethyl peroxides such as benzyl peroxide; tertiary butyl peroxy acetate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy isopropyl Carbonate and other peroxy esters, methyl ethyl ketone peroxide, cyclohexanone peroxide and other ketone peroxides and other organic peroxides; hydrogen peroxide, persulfate, metal oxides and other inorganic peroxides, Azo compounds, mono- and disulfides, metal chelating agents, redox initiators, etc. When using these radical generators, it is preferably 0.01-15 parts by mass, more preferably 0.05-10 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product.

As a sulfur compound, sulfur monochloride, sulfur dichloride, etc. are mentioned, for example. When sulfur or sulfur compounds are used, the content of sulfur or sulfur compounds in the adhesive composition is preferably 0.1-20 parts by mass, more preferably 0.2-10 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product Mass parts.

啉基二硫代)苯并噻唑等噻唑類；二苯基胍、三苯基胍等胍類；丁基醛-苯胺反應物、六亞甲基四胺-乙醛反應物等醛-胺系反應物或醛-氨系反應物、2-巰基咪唑啉等咪唑啉類；二苯硫脲、二乙基脲、二丁基硫脲、三甲基硫脲、二鄰甲苯基硫脲等硫脲類；四甲基秋蘭姆一硫化物、四甲基秋蘭姆二硫化物、五亞甲基秋蘭姆四硫化物等秋蘭姆(thiuram)一或多硫化物類；二甲基二硫胺甲酸鋅、乙基苯基二硫胺甲酸鋅、二甲基二硫胺甲酸鈉、二甲基二硫胺甲酸硒、二乙基二硫胺甲酸碲等二硫胺甲酸鹽類；二丁基黃原酸鋅等黃原酸鹽類、有機過氧化物、鋅華等。此等硫化促進劑可為一種，亦可併用二種以上。併用硫化促進劑之情形，其添加量，相對於嵌段共聚物或其氫化物100質量份，較佳為0.05~30質量份，更佳為0.1~20質量份，再佳為0.2~10質量份。As the vulcanization accelerator, for example, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(4-

Linyl dithio) thiazoles such as benzothiazole; Guanidines such as diphenylguanidine and triphenylguanidine; Aldehyde-amine systems such as butylaldehyde-aniline reactant, hexamethylenetetramine-acetaldehyde reactant Reactants or aldehyde-ammonia reactants, 2-mercaptoimidazoline and other imidazolines; diphenyl thiourea, diethyl urea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl thiourea and other sulfur Urea; thiuram mono- or polysulfide such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, pentamethylenethiuram tetrasulfide, etc.; dimethyl Dithiocarbamates such as zinc dithiocarbamate, zinc ethyl phenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, and tellurium diethyl dithiocarbamate; two Xanthogenates such as zinc butyl xanthogenate, organic peroxides, zinc blooms, etc. These vulcanization accelerators may be one type, or two or more types may be used in combination. When a vulcanization accelerator is used in combination, the amount added is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.2 to 10 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product Copies.

In the case of a sealant, the adhesive composition preferably contains at least one selected from the above-mentioned fillers and additives. In the case of a sealant, it is preferable to use a filler from the viewpoint of vibration damping properties. Examples of the above-mentioned filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate, glass fiber, and carbon fiber. In the case of containing a filler and used as a sealant, the content of the filler in the adhesive composition is preferably 10 to 200 parts by mass, and more preferably 10 to 150, relative to 100 parts by mass of the block copolymer or its hydrogenated product Mass parts. Among the additives, it is preferable to use a lubricant from the viewpoint of improving the fluidity of the sealant while suppressing thermal degradation. Examples of lubricants include: silicone oil; hydrocarbon lubricants such as paraffin wax, microcrystalline wax, and polyethylene wax; butyl stearate, stearic acid monoglyceride, neopentyl erythritol tetrastearate, and stearin. Stearyl acid. In the case of containing a lubricant and acting as a sealant, the content of the lubricant in the adhesive composition is preferably 1-20 parts by mass, more preferably 1-15 parts by mass relative to 100 parts by mass of the block copolymer or its hydrogenated product Mass parts.

[other] In this embodiment, the adhesive and hot melt adhesive including the adhesive composition can be used for various purposes. Adhesives and hot melt adhesives, for example: Used in disposable diapers, adult incontinence products, sanitary napkins, mattresses, bandages, surgical drape (surgical drape), single-sided tape, double-sided tape, transfer tape, labels, plastic sheets, non-woven sheets, paper sheets, cardboard, Use in books, filters or articles with packaging; Use in gasket sealants (especially in the fields of automobiles, motor parts, and technical lighting); Use in the manufacture of multi-layer film resealable trays; Use in articles containing materials for mailing containers; In anti-vibration materials, cushioning materials, shock-absorbing materials, low-rebound materials, anti-falling materials, shock-proof materials, shock-proof materials, or vibration-damping materials (preferably sound-absorbing materials, more preferably attenuating or sound-absorbing mats in the automotive industry, Liner, sheet and tape); Use in electronic devices (especially LCD displays, LED displays, touch screens, or flexible thin-film solar cells); Use in transdermal drug delivery systems; Between conduits (preferably cooling coils), electronic parts (preferably light-emitting parts, computer equipment, mobile phones, tablets, touch screens, automotive technology high-fidelity systems, and audio systems), solar heating heat pipes and water tanks Combinations of fuel cells and wind turbines, computer chip manufacturing, optical devices, batteries, cabinets, coolers, heat exchange devices, wires, cables, heating wires, refrigerators, dishwashers, air-conditioning equipment, batteries, transformers , Laser equipment, functional clothing, car seats, medical equipment, fire protection devices, electric motors, airplanes, and trains; Use in filaments of 3D printing materials, sealants or molding sealants for sealing heating devices; The use of joining objects with substrates formed of wood, metal, polymer plastic, glass and textiles; the use of joining to the outside in the water supply tower; as in the manufacture of footwear Or use of glaze in the manufacture of windows, in the manufacture of doors and building panels, or in the manufacture of portable devices and displays; Used in binding, wood bonding, flat lamination, flexible packaging, profile wrapping, edge banding, textile lamination, low-pressure forming, and shoes; Use in the manufacture of books, packaging films, rigid panels, furniture, windows, footwear, car headlights, car trims, or bonded fabrics/fabrics for clothing; Use in decorative film. [Example]

Hereinafter, the present invention will be explained more specifically with examples and comparative examples, but the present invention is not limited to these.

The method for evaluating the physical properties of the hydrogenated block copolymer obtained in the production example described below is disclosed below. (1) Content of polymer block (A) The block copolymer before hydrogenation was dissolved in CDCl ₃ and ^{measured by 1} H-NMR [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 °C], the content of the polymer block (A) was calculated from the ratio of the peak intensity derived from styrene to the peak intensity derived from diene.

(2) Weight average molecular weight (Mw) According to the gel permeation chromatography (GPC) measurement under the following conditions, the weight average molecular weight (Mw) in terms of polystyrene is calculated for the hydrogenated product of the block copolymer. (GPC measuring device and measuring conditions) ・Device: GPC device "HLC-8020" (manufactured by Tosoh Co., Ltd.) ・Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Co., Ltd. are connected in series. ・Separation liquid: Tetrahydrofuran ・Separate flow rate: 0.7mL/min ・Sample concentration: 5mg/10mL ・Column temperature: 40℃ ・Detector: Differential refractive index (RI) detector ・Calibration line: made using standard polystyrene

(3) The hydrogenation rate in the polymer block (B) was ^{measured by 1} H-NMR, and the peak area of the residual olefin derived from isoprene and/or butadiene was compared with the peak area derived from ethylene, propylene and/or butene. Calculated by the ratio of the peak area.・Device: Nuclear magnetic resonance device "ADVANCE 400 Nano bay" (manufactured by Bruker) ・Solvent: CDCl ₃

(4) Vinyl bonding amount in polymer block (B) The block copolymer before hydrogenation is dissolved in CDCl ₃ and ^{measured by 1} H-NMR [device: "ADVANCE 400 Nano bay" (manufactured by Bruker) , Measurement temperature: 30℃]. From the total peak area of the structural unit derived from isoprene and/or butadiene, and the 3,4-bonding unit, 1,2-bonding unit and butadiene structural unit in the isoprene structural unit In the 1,2-bonding unit, or in the case of a structural unit derived from a mixture of isoprene and butadiene, the ratio of the peak area of each aforementioned bonding unit is calculated, and the vinyl bonding amount is calculated ( The total content of 3,4-bonding unit and 1,2-bonding unit).

(5) The content of the alicyclic skeleton (X) in the polymer block (B). Dissolve 600 mg of the block copolymer before hydrogenation and 40 mg of _{Cr(acac) 3 in 4 mL of CDCl 3} and use a 10 mm NMR tube to quantify ¹³ C-NMR measurement (pulse program: zgig, Inverse gated 1H decoupling method) [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C], the polymer block was calculated by the following method ( The content of each of the alicyclic skeleton X, X1, and X2 in B). In addition, in Table 3, X, X1, and X2 represent the following alicyclic skeletons. X: an alicyclic skeleton having a combination of the following (i) to (vi) substituents X1: an alicyclic skeleton having a combination of the following (i) and (iv) substituents X2: having the following (ii), (iii) The alicyclic skeleton (i) of the combination of substituents of (v) and (iv): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Bd+Bd) (ii): R ¹ = hydrogen atom, R ² = methyl, R ³ = hydrogen atom; (1,2Bd+1,2Ip) (iii): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = Methyl; (1,2Bd+3,4Ip) (iv): R ¹ = methyl, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Ip+Bd) (v): R ¹ = methyl , R ² = methyl, R ³ = hydrogen atom; (1,2Ip+1,2Ip) (vi): R ¹ = methyl, R ² = hydrogen atom, R ³ = methyl; (1,2Ip+3 ,4Ip)

[Calculation method] The peaks and their derived structures are disclosed in Table 1-1. If the integral value of each peak is set as a~g, the integral value of each structure becomes as shown in Table 1-2, and the content of X, X1, and X2 can be expressed as (a+gc)/(a+b+c -d+e/2+2f), (gc)/(a+b+c-d+e/2+2f), a/(a+b+c-d+e/2+2f).

[Table 1] Table 1-2 Table 1-1 structure Integral value Peak (ppm) structure Integral value St df 108~110 X2 a 1,4Ip f 110~113 3,4Ip+1,2Ip+X1 b 3,4Ip+1,2Ip b-(gc) 113~116 1,2Bd c 1.4Bd (e-(df)×4)/2 122~127 1,4Ip+St d 1,2Bd c 127~132 1,4Bd×2+St×4 e X1 gc 132~137 1,4Ip f X2 a 142~145 1,2Bd+X1 g total a+b+c-d+e/2+2f

(6) ^{Peak area ratio of 13} C-NMR For the hydrides of Production Example 1 and Comparative Production Example 1, the above-mentioned quantitative ¹³ C-NMR measurement was performed [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), and measurement temperature: 30°C, solvent: CDCl ₃ ], calculate the peak area ratio [peak area with chemical shift value 50.0-52.0 ppm]/[peak area with chemical shift value 43.0-45.0 ppm].

(7) Peak top temperature of tanδ, peak top intensity, the maximum width of the temperature range where tanδ becomes 1.0 or more, and the tanδ intensity at 20°C and 30°C For the following measurement, the hydrogenated product of the block copolymer was pressed at a temperature of 230°C and a pressure of 10 MPa for 3 minutes to produce a single-layer sheet with a thickness of 1.0 mm. This single-layer sheet was cut into a circular plate shape, and this was used as a test piece. In the measurement, based on JIS K 7244-10 (2005), a strain-controlled dynamic viscoelastic device "ARES-G2" (manufactured by TA Instruments Japan Co., Ltd.) with a circular plate diameter of 8 mm was used as a parallel plate vibration rheometer. With the above test piece, the gap between the two plates is completely filled, and the strain is 0.1%. The above test piece is vibrated at a frequency of 1 Hz, and the temperature is raised from -70°C to 100°C at a constant rate of 3°C/min. . Until the measured values of the shear loss modulus and the shear storage modulus do not change, keep the temperature of the test piece and the disc, and obtain the maximum value of the peak intensity of tanδ (peak top intensity) and the temperature at which the maximum value is obtained (Peak top temperature). In addition, the tanδ intensity at 20°C and 30°C, which is the maximum width of the temperature region where tanδ becomes 1.0 or more, is obtained. The larger the value, the better the vibration damping performance.

[Manufacturing Example 1] Manufacturing of hydride (H-TPE-1) In a dry pressure vessel that has been substituted with nitrogen, 50 kg of cyclohexane is filled as a solvent, and 87 g of a cyclohexane solution of secondary butyl lithium with a concentration of 10.5% by mass (the actual amount of secondary butyl lithium added: 9.1 g) As an anionic polymerization initiator. After raising the temperature in the pressure vessel to 50°C, add 1.0 kg of styrene (1) to polymerize for 1 hour, and add 2,2-bis(2-tetrahydrofuryl)propane as the Lewis base at a temperature of 50°C in the vessel (DTHFP) 63g, a mixture of 8.16kg isoprene and 6.48kg butadiene was added using the average diene feed rate shown in Table 2. After 5 hours of addition, it was polymerized for 2 hours, and then styrene was added (2) 1.0 kg was polymerized for 1 hour to obtain a reaction liquid containing a polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer. In this reaction solution, a Chigler-based hydrogenation catalyst composed of nickel octoate and trimethylaluminum was added in a hydrogen gas atmosphere, and the reaction was carried out for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C. After allowing the reaction solution to cool down and releasing the pressure, the catalyst was removed by washing with water and dried in a vacuum, thereby obtaining a polystyrene-poly(isoprene/butadiene)-polystyrene triblock The hydrogenated product of the copolymer (hereinafter, sometimes referred to as H-TPE-1). About each raw material and its usage amount, it is shown in Table 2. In addition, the results of the aforementioned physical property evaluation are shown in Table 3.

[Comparative Manufacturing Example 1] Manufacturing of hydride (H-TPE-1’) Except for changing the usage amounts of the components and the like, and the reaction conditions as described in Table 2, the same procedure as in Production Example 1 was carried out to produce a hydrogenated block copolymer (H-TPE-1'). In addition, the results of the aforementioned physical property evaluation are shown in Table 3.

[Table 2] Manufacturing example Comparative manufacturing example 1 1 Hydride of block copolymer H-TPE-1 H-TPE-1' Usage (kg) Cyclohexane 50 50 Secondary butyl lithium (10.5 mass% cyclohexane solution) 0.087 0.087 (A) Styrene (1) 1.0 1.0 Styrene (2) 1.0 1.0 (B) Isoprene 8.16 14.64 Butadiene 6.48 0 Lewis base DTHFP 0.063 0 Reaction conditions Diene polymerization temperature (℃) 50 50 Diene feed time (h) 5 5 Average feed rate of diene per 1 mol of active end (kg/h) 20.5 20.5

[table 3] Manufacturing example Comparative manufacturing example 1 1 Hydrogenated block copolymer used H-TPE-1 H-TPE-1' Structural unit of polymer block (A) St St Components constituting the polymer block (B) Ip/Bd Ip The mass ratio of the components constituting the polymer block (B) 55/45 100 The molar ratio of the components constituting the polymer block (B) 50/50 100 Polymer structure A/B/A A/B/A Content of polymer block (A) (mass%) 12 12 Weight average molecular weight of hydrogenated block copolymer 167,000 160,000 Hydrogenation rate in polymer block (B) (mol%) 95 99 Vinyl bond amount in polymer block (B) (mol%) 76 5 The content of X1 or X1 hydride in block (B) (mol%) 5 0 The content of X2 or X2 hydride in block (B) (mol%) 9.9 0 The content of X or X hydride in block (B) (mol%) 14.9 0 ¹³ C-NMR area ratio after hydrogenation [50~52ppm peak area]/[43~45ppm peak area] 0.21 0 Peak top temperature of tanδ (℃) 14.9 -55.2 Peak top intensity of tanδ 2.24 2.35 Become the maximum range of the temperature zone where tanδ≧1 (℃) 17.9 6.0 Tanδ intensity at 20℃, 1Hz 1.70 0.06 Tanδ intensity at 30℃, 1Hz 0.81 0.07

The block copolymer of Production Example 1 and its hydrogenated product showed a peak top strength of tanδ of 1.0 or more, and showed a peak top temperature of tanδ in a wide temperature range, and therefore can be said to be suitable for use as a vibration damping material in a wide range of applications. In particular, when compared with Comparative Production Example 1, it can be seen that in Production Example 1, the tanδ strength at 20°C and 30°C is relatively high, and the vibration damping properties around room temperature are excellent.

＜Adhesive composition＞ [Examples 1 to 5] [Comparative examples 1 to 5] (Method of making adhesive composition <1>) According to the composition shown in Table 4, compared with the hydrogenated product (H-TPE-1, H-TPE-1') of the block copolymer obtained in the aforementioned Production Example 1 and Comparative Production Example 1, adhesion-imparting resin and plasticizing The total amount of the agent and the antioxidant (additive) is added with the same parts by mass of toluene to prepare a toluene solution. Using a Baker applicator (SA-201, manufactured by TESTER SANGYO Co., Ltd.), the toluene solution was applied to a 50μm thick polyethylene terephthalate (PET) film (trade name Teijin Tetoron Film). G2, manufactured by Teijin DuPont Films Co., Ltd.), dried at 60°C for 30 minutes to produce an adhesive composition on the PET film. The thickness of the adhesive composition is 30 μm.

(Method of making adhesive composition <2>) After preparing the toluene solution in the same manner as in the above (Method of Making Adhesive Composition <1>), add 5 g of the toluene solution to a cardboard box measuring 5 cm in length × 5 cm in width × 3 cm in height (with the release PET side as the inner side), and heat it at 23°C It was dried for 24 hours and then dried at 60° C. for 8 hours to produce an adhesive composition. The thickness of the adhesive composition is 1 mm.

[Example 6] [Comparative Example 6] (Method of making adhesive composition <3>) According to the composition shown in Table 4, the hydrogenated product (H-TPE-1, H-TPE-1') of the block copolymer obtained in the aforementioned Production Example 1 and Comparative Production Example 1, adhesion-imparting resin, plasticizer, Fillers and antioxidants (additives) are put into a Brabender (manufactured by Brabender, "Plastograph EC 50cc mixer"), and melt-kneaded for 3 minutes at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm After that, the obtained composition was inserted into a 50 μm thick polyethylene terephthalate (PET) film (trade name Teijin Tetoron Film G2, manufactured by Teijin DuPont Films Co., Ltd.) on one side and press-molded (200°C, 2 minutes), thereby manufacturing an adhesive composition on the PET film. The thickness of the adhesive composition is 0.5 mm.

(Method of making adhesive composition <4>) After melting and kneading in the same manner as in the above (Method of Making Adhesive Composition <3>), the obtained composition was press-molded (200°C, 2 minutes) to produce an adhesive composition. The thickness of the adhesive composition is 1 mm.

[Physical Property Evaluation] The evaluation method of the physical properties of the adhesive composition produced above is disclosed below. (Tanδ peak top temperature, peak top strength, shear storage modulus at 23°C, 60°C, tanδ strength at 23°C, 40°C, 60°C, complex viscosity at 60°C (shear, 1Hz)) The measurement is performed in accordance with JIS K 7244-10 (2005). Specifically, the adhesive composition obtained by the above (Method of Making Adhesive Composition <2>) (Method of Making Adhesive Composition <4>) was cut into a disc shape with a diameter of 8 mm as a sample and used The strain-controlled dynamic viscoelastic device "ARES-G2" (manufactured by TA Instruments) clamps the aforementioned sample on a flat plate with a diameter of 8 mm, and vibrates with a strain amount of 0.1% and a frequency of 1 Hz. The temperature is 3°C/min from -70°C The temperature was raised to 180°C and the measurement was performed to measure the peak top temperature of tanδ, peak top strength, shear storage modulus (G') at 23, 60°C, tanδ intensity at 23°C, 40°C, and 60°C. Complex viscosity at 60°C. The results are shown in Table 4.

(Shore A hardness) The adhesive composition obtained by the above (Method of Making Adhesive Composition <4>) was superimposed on 6 pieces respectively, and used as a test piece for hardness measurement with a thickness of 6mm. According to JIS K 6253 (2012), an automatic rubber hardness tester P2 was used. -Type A (manufactured by Polymer Meter) to measure the hardness of the adhesive composition. The results are shown in Table 4.

(Peel strength at 23°C) Acrylic extrusion sheet (trade name SUMIPEX E, thickness 1.5mm, manufactured by SUMIKA ACRYL Sales Co., Ltd.) is made of (Method of Making Adhesive Composition <1>) (Method of Making Adhesive Composition <3> ) The obtained adhesive composition was attached so as to face the acrylic resin board, and the one cut into a width of 25 mm was used as a test piece. Thus, the polyethylene terephthalate side of the test piece, using a 2kg rubber roller, was reciprocated and pressed twice at a speed of 10mm/min, and then placed in a gas environment at 23±1°C and a humidity of 50±5%. hour. Thereafter, in accordance with JIS Z 0237 (2009), using INSTRON 5566 (manufactured by INSTRON), the 180-degree peel strength between the adhesive composition and the acrylic resin plate was measured at a peeling speed of 300 mm/min, as the peeling strength at 23°C. strength. The results are shown in Table 4.

(Peel strength at 60℃) After leaving for 24 hours in a 23±1°C and 50±5% humidity gas environment, and then placing it in a 60°C gas environment for 10 minutes, measure the peel strength in a 60°C gas environment. Otherwise, it is the same as the above (Peel strength at 23°C) The same was performed, and it was taken as the peel strength at 60°C. The results are shown in Table 4.

[Table 4] Example Comparative example 1 2 3 4 5 6 1 2 3 4 5 6 Composition (parts by mass) H-TPE-1 100 100 100 100 100 100 0 0 0 0 0 0 H-TPE-1' 0 0 0 0 0 0 100 100 100 100 100 100 Adhesive imparting resin (1) 150 200 0 300 300 0 150 200 0 300 300 0 Adhesion imparting resin (2) 0 0 150 0 0 150 0 0 150 0 0 150 Plasticizer 100 100 100 150 170 200 100 100 100 150 170 200 Filler 0 0 0 0 0 100 0 0 0 0 0 100 Antioxidants 1 1 1 1 1 1 1 1 1 1 1 1 Physical properties Peak top temperature of tanδ (℃) 5.2 13.7 13.7 14.2 12.4 -8.4 -15.9 -4.8 -11.4 4.5 2.9 -20.9 Peak top intensity of tanδ 3.69 4.11 3.23 4.96 4.86 3.19 2.31 2.49 1.82 3.16 2.67 2.15 tanδ intensity (23℃) 1.11 2.61 2.01 3.51 2.69 0.60 0.08 0.23 0.12 0.58 0.39 0.11 tanδ intensity (40℃) 0.39 0.69 0.61 0.92 0.72 0.31 0.06 0.08 0.07 0.13 0.13 0.09 tanδ intensity (60℃) 0.28 0.33 0.30 0.48 0.49 0.34 0.09 0.10 0.08 0.15 0.17 0.13 Complex viscosity (60℃)(Pa·s) 3000 3150 3960 1760 1300 2190 9110 9520 13,700 4880 3490 9590 Shaw A Hardness - - - - - 5 - - - - - 3 G'(23℃)(Pa) 42600 82500 84100 56400 32800 25500 55100 60200 86400 35300 25600 62800 G'(60℃)(Pa) 18200 18700 23800 9900 7300 13000 57000 59600 85900 30300 21600 59700 G'(23℃)/G'(60℃) 2.34 4.41 3.53 5.70 4.49 1.96 0.97 1.01 1.01 1.16 1.19 1.05 Peel strength (23℃)(N/25mm) 18.3 28.4 20.4 32.6 24.1 14.9 13 20.2 18.3 1.55 21.8 4.2 Peel strength (60℃)(N/25mm) 11.3 12.8 15.1 7.3 5.1 6.1 2.1 2.6 7.4 0.16 0.70 1.4 Peel strength ratio (60℃/23℃) 0.62 0.45 0.74 0.22 0.21 0.41 0.16 0.13 0.40 0.10 0.03 0.33

The components shown in Table 4 are as follows. ・Adhesive resin: Alcon P-100 (alicyclic saturated hydrocarbon resin, softening point (ball and ball method) 100±5°C, manufactured by Arakawa Chemical Industry Co., Ltd.) ・Adhesive resin: Alcon P-125 (alicyclic saturated hydrocarbon resin, softening point (ring and ball method) 125±5°C, manufactured by Arakawa Chemical Industry Co., Ltd.) ・Plasticizer: Diana Process Oil PW-90 (hydrogenated paraffin-based processing oil, manufactured by Idemitsu Kosan Co., Ltd.) ・Filling agent: Escalon#200 (Heavy calcium carbonate, manufactured by Sankyo Fine Powder Co., Ltd.) ・Antioxidant: ADK STAB AO-60 (hindered phenol antioxidant, manufactured by ADEKA Co., Ltd.)

From Table 4, compared with the adhesive composition of Comparative Examples 1 to 6, the peak top strength of the tanδ of the adhesive composition of Examples 1 to 6 is larger. In the temperature range of 23 to 60°C, the tanδ The value of intensity is larger. In addition, compared with the adhesive compositions of Comparative Examples 1 to 6, the adhesive compositions of Examples 1 to 6 have a lower complex viscosity at 60°C. Furthermore, compared with the adhesive compositions of Comparative Examples 1 to 6, the storage modulus G'ratio of the adhesive compositions of Examples 1 to 6 [G'(23°C)/G'(60°C)] Larger, 1.5 or more. In this way, the ratio of the storage modulus at 23°C to 60°C of the adhesive composition of the example is greater than that of the comparative example, and the peel strength at 23°C to 60°C decreases less [(peel strength at 60°C)/(in The peel strength at 23°C) is large]. Therefore, it can be seen that the adhesive composition of the examples has excellent vibration damping properties, handling properties, and hydrides by containing the block copolymer or its hydrogenated product having a structural unit containing an alicyclic skeleton (X) in the main chain. Adhesiveness, and maintains adhesiveness even under high temperature conditions.

In addition, although it is not clear, it can be assumed that the adhesive composition containing the block copolymer or its hydrogenated product will be softened at high temperature (60°C). Therefore, the following conditions suppress the adhesion between the adhesive composition and the bonded material Decrease of adhesive force: It penetrates into the small irregularities on the surface of the material to be bonded (acrylic resin sheet) and acts like an anchor, or the surface of the adhesive composition is in contact with the surface of the material to be bonded. It fits into the recess of the material to be bonded and exerts an elastic tightening force. In addition, the adhesive composition of Example 6 had a low Shore A hardness. Therefore, it can be seen that the adhesive composition of the embodiment containing the filler contains the block copolymer or its hydrogenated product having a structural unit containing an alicyclic skeleton (X) in the main chain, and has a sealant Excellent vibration damping, handling and adhesion, and maintain adhesion even under high temperature conditions. [Industry Availability]

Since the adhesive composition of the present invention has vibration damping properties and has adhesive properties that are not easy to peel off even at high temperatures, it is useful as an adhesive, especially a hot melt adhesive. In addition, the adhesive composition of the present invention can also be used as a sealant.

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Claims (20)

An adhesive composition containing at least 1 selected from 1 to 1000 parts by mass of adhesion-imparting resin and 1 to 1000 parts by mass of plasticizer relative to 100 parts by mass of the following block copolymer or its hydrogenated product Species; The aforementioned block copolymer contains a polymer block (A) and a polymer block (B), the polymer block (B) is a structural unit derived from a conjugated diene compound, and has the following in the main chain One or more structural units of alicyclic skeleton (X) represented by formula (X);

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different). Such as the adhesive composition of claim 1, which contains 120 to 1000 parts by mass of the aforementioned adhesive imparting resin. Such as the adhesive composition of claim 1 or 2, which contains 60 to 1000 parts by mass of the aforementioned plasticizer. The adhesive composition according to any one of claims 1 to 3, which further contains 10 to 2500 parts by mass of a filler. The adhesive composition according to any one of claims 1 to 4, wherein the aforementioned alicyclic skeleton (X) contains ^{at least one of the aforementioned R 1} to R ³ being a hydrocarbon group with 1 to 11 carbons The alicyclic skeleton (X'). The adhesive composition of claim 5, wherein the hydrocarbon group in the alicyclic skeleton (X') is a methyl group. The adhesive composition according to any one of claims 1 to 6, which at least contains a styrene-hydrogenated butadiene/isoprene-styrene copolymer as the hydrogenated product of the aforementioned block copolymer. An adhesive composition according to any one of claims 1 to 4, wherein the aforementioned R ¹ to R ³ are hydrogen atoms at the same time. The adhesive composition according to any one of claims 1 to 8, which contains 1 mol% or more of the alicyclic skeleton (X) in the polymer block (B). Such as the adhesive composition of claim 5 or 6, which contains 1 mol% or more of the alicyclic skeleton (X') in the polymer block (B). The adhesive composition according to any one of claims 1 to 10, wherein the hydrogenation rate of the polymer block (B) is 0 mol% or more and less than 50 mol%. The adhesive composition according to any one of claims 1 to 10, wherein the hydrogenation rate of the polymer block (B) is 50 to 99 mol%. The adhesive composition according to any one of claims 1 to 12, wherein the vinyl bond amount in the polymer block (B) is 55 to 95 mol%. Such as the adhesive composition of any one of claims 1 to 13, wherein the aforementioned block copolymer or its hydrogenated product exists: in accordance with JIS K 7244-10 (2005), the amount of strain is 0.1%, the frequency is 1 Hz, and the measurement The tanδ measured under the conditions of a temperature of -70 to 100°C and a temperature increase rate of 3°C/min becomes a continuous temperature range of 1.0 or more; the maximum range of this temperature range is 13°C or more. The adhesive composition according to any one of claims 1 to 14, wherein the aforementioned polymer block (A) contains more than 70 mol% of structural units derived from aromatic vinyl compounds. The adhesive composition according to claim 15, wherein the content of the polymer block (A) in the block copolymer is 50% by mass or less. The adhesive composition according to claim 15, wherein the content of the polymer block (A) in the block copolymer is 16% by mass or less. The adhesive composition according to any one of claims 1 to 17, wherein the shear storage modulus G'(23°C) at 23°C is relative to the shear storage modulus G'(60°C) at 60°C The ratio [G'(23°C)/G'(60°C)] is 1.3 or more. An adhesive comprising the adhesive composition according to any one of claims 1 to 18. A sealant comprising the adhesive composition as claimed in claim 4.