WO2020235661A1 - 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 a viscous adhesive composition containing a block copolymer or a hydrogenated product thereof.

Block copolymers having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound and their hydrogenated products have vibration damping properties. It is already known that some of them have, and have been used as damping materials. In addition, the block copolymer and its hydrogenated additive may have physical properties such as sound insulation, heat resistance, impact resistance, and adhesiveness in addition to vibration damping properties, and there are various types. It is conceivable that it can be used for various purposes.
For example, styrene compounds and isoprene, butadiene, etc., whose peak temperature of tan δ and vinyl bond amount are specified in order to improve mechanical properties such as vibration damping, flexibility, heat resistance, tensile strength and impact resistance. Hydrogenated block copolymers with conjugated diene compounds are disclosed (see, for example, Patent Documents 1 to 4).

It is known that block copolymers having a long open time and exhibiting good adhesiveness are used, for example, as adhesives for diapers and non-woven fabrics, and as adhesives for surface protective films such as electrical and electronic parts. (See, for example, Patent Document 5).
Further, it is known that among the block copolymers, those exhibiting vibration damping properties and adhesive properties can be used, for example, as sealants in the fields of automobiles and construction (see, for example, Patent Document 6).

Japanese Unexamined Patent Publication No. 2002-284830 International Publication No. 2000/015680 Japanese Unexamined Patent Publication No. 2006-117879 Japanese Unexamined Patent Publication No. 2010-0533319 International Publication No. 2002/040611 International Publication No. 2015/087954

On the other hand, the adherend bonded via the adhesive may be peeled off by vibration, and improvement in the performance of the adhesive is required. Further, the adhesive strength tends to decrease as the temperature rises, and it is desired that the adhesive strength is maintained even at a high temperature.
Therefore, it is desired that the adhesive strength is not easily peeled off from the adherend and the adhesive strength is maintained even at a high temperature, and there is room for improvement in the adhesive composition for both vibration damping and adhesiveness. is there.
Therefore, the present invention provides a viscous adhesive composition that has vibration damping properties and is not easily peeled off even at high temperatures.

As a result of diligent studies to solve the above problems, the present inventors have conceived the following inventions and found that the problems can be solved.
That is, the present invention is as follows.

A viscous adhesive composition containing at least one selected from 1 to 1000 parts by mass of a tackifier resin and 1 to 1000 parts by mass of a plasticizer with respect to 100 parts by mass of the following block copolymer or hydrogenated product thereof.
The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.

(In the above formula (X), R ¹ to R ³ 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.)

According to the present invention, it is possible to provide a viscous adhesive composition having vibration damping properties and which is hard to peel off even at a high temperature.

≪Adhesive composition≫
The adhesive composition of the present invention is at least one selected from 1 to 1000 parts by mass of a tackifier resin and 1 to 1000 parts by mass of a plasticizer with respect to 100 parts by mass of the following block copolymer or hydrogenated product thereof. It is characterized by including.
The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound, and the formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.
Each component contained in the adhesive composition will be described below.

[Block copolymer or hydrogenated product thereof]
In an embodiment of the present invention (hereinafter, may be referred to as "the present embodiment"), the block copolymer or a hydrogenated product thereof has vibration damping properties and is a viscous adhesive composition that is difficult to peel off even at high temperatures. It is an essential ingredient for
[Polymer block (A)]
The polymer block (A) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer from the viewpoint of vibration damping and mechanical properties.
The polymer block (A) contains more than 70 mol% of a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as “aromatic vinyl compound unit”) in the polymer block (A). 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 100 mol% or more. ..

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, and 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, 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-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, m -T-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethyl Examples thereof include styrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, inden, vinylnaphthalene, N-vinylcarbazole and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of production cost and physical property balance.

The polymer block (A) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter, “other unsaturated monomer unit”” as long as it does not interfere with the object and effect of the present invention. It may be abbreviated as), but it is preferably 30 mol% or less, more preferably less than 20 mol%, still more preferably less than 15 mol%, still more preferably less than 30 mol% in the polymer block (A). It is less than 10 mol%, more preferably less than 5 mol%, and particularly preferably 0 mol%.
Examples of the other unsaturated monomer include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8, At least one selected from the group consisting of 9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran and the like can be mentioned. When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited and may be random or tapered.

The block copolymer may have at least one of the polymer blocks (A). When 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 polymer block is different" means the monomer unit constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio of each monomer unit when having a plurality of monomer units. It means that at least one of the forms of polymerization (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) contained in the block copolymer is , Preferably 3,000 to 60,000, more preferably 4,000 to 50,000. When the block copolymer has at least one polymer block (A) having a weight average molecular weight within the above range, it can contribute to further improvement of vibration damping property.
The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement.

(Content of polymer block (A))
The content of the polymer block (A) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 16% by mass or less, and 14% by mass. It is particularly preferable that it is% or less. If it is 50% by mass or less, it can be a block copolymer having appropriate flexibility and excellent vibration damping property without lowering the tan δ peak top strength or a hydrogenated additive thereof. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 6% by mass or more. If it is 1% by mass or more, it can be a block copolymer having mechanical properties, molding processability, coatability and the like suitable for various uses of the adhesive composition, or a hydrogenated additive thereof. ..
The content of the polymer block (A) in the block copolymer is a value obtained by ^{1 1} H-NMR measurement, and more specifically, a value measured according to the method described in Examples.

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

In the above formula (X), R ¹ to R ³ 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 from each other. The hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 (that is, a methyl group). Further, the hydrocarbon group may be a straight chain or a branched chain, or may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), it is particularly preferable that R ¹ to R ³ are independently hydrogen atoms or methyl groups, respectively.
When the block copolymer is hydrogenated, the vinyl group in the above formula (X) can be hydrogenated. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated additive also includes the skeleton in which the vinyl group in the above formula (X) is hydrogenated.

The polymer block (B) is a structural unit derived from the conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound by a method described later, and at least one alicyclic skeleton (X) is the main alicyclic skeleton-containing unit depending on the conjugated diene compound used. Included in the chain. Since the alicyclic skeleton (X) is incorporated into the main chain of the structural unit contained in the polymer block (B), the molecular motion is reduced and the glass transition temperature rises, so that tan δ at around room temperature The peak top strength is improved, and excellent vibration damping properties can be exhibited.

Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-pentadiene. , 1,3-Hexadiene, 1,3-octadien, 1,3-cyclohexadiene, 2-methyl-1,3-octadene, 1,3,7-octatriene, farnesene, milsen, chloroprene and the like. .. Of these, butadiene, isoprene, or a combination of butadiene and isoprene is preferable.

When butadiene and isoprene are used in combination, the blending ratio [isoprene / butadiene] (mass ratio) thereof is not particularly limited, but is preferably 5/95 to 95/5, more preferably 10/90 to 90/10. It is more preferably 40/60 to 70/30, and particularly preferably 45/55 to 65/35. When the mixing ratio [isoprene / butadiene] is expressed in molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, particularly. It is preferably 45/55 to 55/45.

As a specific example, an alicyclic skeleton (X) 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 the following combination of substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) is only an alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms at the same time. Therefore, as an example of a preferred embodiment of the block copolymer or its hydrogenated product, the polymer block (B) has one alicyclic skeleton (X) in which R ¹ to R ³ are hydrogen atoms at the same time as the main chain. Examples include those having a structural unit contained in.

When isoprene is used alone as the conjugated diene compound, two types of alicyclic skeletons (X) having a combination of the following substituents (v) and (vi) are mainly produced.
When butadiene and isoprene are used in combination as the conjugated diene compound, six types of alicyclic skeletons (X) having a combination of the following substituents (i) to (vi) are mainly produced.
(I): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom (ii): R ¹ = hydrogen atom, R ² = methyl group, R ³ = hydrogen atom (iii): R ¹ = hydrogen Atomic, R ² = hydrogen atom, R ³ = methyl group (iv): R ¹ = methyl group, R ² = hydrogen atom, R ³ = hydrogen atom (v): R ¹ = methyl group, R ² = methyl group, R ³ = hydrogen atom (vi): R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group

In the above formula (X), at least one alicyclic skeleton in the polymer block (B) from the viewpoint that the molecular motion becomes smaller and the vibration damping property is further improved by having a substituent which is a hydrocarbon group. (X) is preferably an alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a hydrocarbon group having 1 to 11 carbon atoms. Among them, the alicyclic skeleton can be efficiently generated from the conjugated diene compound, and the hydrocarbon group in the alicyclic skeleton (X') is a methyl group from the viewpoint of the balance between vibration damping property and mechanical properties. Is more preferable.
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 alicyclic skeletons that are not hydrogen atoms at the same time. That is, it is more preferable that the polymer block (B) has a structural unit containing at least one of the alicyclic skeletons having a combination of the substituents (ii) to (vi) in the main chain. ..

(Amount of vinyl bond in polymer block (B))
When the structural unit constituting the polymer block (B) is any of an isoprene unit, a butadiene unit, and a mixture unit of isoprene and butadiene, isoprene and butadiene other than the bonded form forming the alicyclic skeleton (X). In the case of butadiene, 1,2-bond and 1,4-bond are taken, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond are taken. Can be done.

In the block copolymer and its hydrogenated product, the content of the 3,4-bonding unit and the 1,2-bonding unit in the polymer block (B) (hereinafter, may be simply referred to as "vinyl bond amount"). The total of.) Is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, still more preferably 66 to 95 mol%, still more preferably 70 to 95 mol%. Within the above range, excellent vibration damping properties can be exhibited. Further, as the vinyl bond amount increases, the peel strength of the adhesive composition tends to be suppressed from decreasing due to an increase in temperature, and the adhesive composition becomes more difficult to peel at a high temperature.
Here, the vinyl bond amount is a value calculated by ¹ H-NMR measurement according to the method described in Examples.
When the polymer block (B) is composed only of butadiene, the above-mentioned "contents of 3,4-bonding unit and 1,2-bonding unit" is "content of 1,2-bonding unit". And apply.

(Alicyclic skeleton (X) content)
The polymer block (B) may contain a structural unit containing an alicyclic skeleton (X) in the main chain, but it exhibits a better anti-vibration effect and has a viscous adhesive force even at high temperatures. The polymer block (B) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, and further preferably 1.1 mol% or more, from the viewpoint of facilitating the suppression of the decrease in the amount. Is 1.4 mol% 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. Is. Further, as the content of the alicyclic skeleton (X) increases, the peel strength of the alicyclic skeleton tends to be suppressed from decreasing due to an increase in temperature, and the alicyclic skeleton becomes even more at high temperature. It becomes difficult to peel off.
The upper limit of the content of the alicyclic skeleton (X) in the polymerization block (B) is not particularly limited as long as it does not impair the effects of the present invention, but is 40 mol% from the viewpoint of productivity. It is preferably 30 mol% or less, 20 mol% or less, and 18 mol% or less.
From the viewpoint of further improving the vibration damping property, it is more preferable that the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X'), and more preferably 1.3 mol% or more. , More preferably 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 alicyclic skeleton (X).

More specifically, when isoprene is used as the conjugated diene compound, when butadiene is used, or when butadiene and isoprene are used in combination, the alicyclic skeleton content in each case is as follows.
When isoprene is used as the conjugated diene compound, when one or more alicyclic skeletons (X') having a combination of the substituents (v) and (vi) are present in the polymer block (B). The total content of these compounds is preferably 1 mol% or more from the viewpoint of exhibiting a more excellent anti-vibration effect and easily suppressing a decrease in adhesive strength even at high temperatures, preferably 1.5 mol%. More preferably, it is more preferably 2 mol% or more, further preferably 3 mol% or more, and 4 mol% or more from the viewpoint of obtaining an excellent anti-vibration effect in a wide temperature range. Is particularly preferable. Further, the upper limit of the total content when isoprene is used is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene is used as the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B) when it is present is 5 mol% or more, which is more excellent vibration damping. It is preferable from the viewpoint of exhibiting a sexual effect and easily suppressing a decrease in adhesive strength even at a high temperature, more preferably 10 mol% or more, further preferably 15 mol% or more, and 20 mol% or more. It is even more preferably 25 mol% or more, and particularly preferably 30 mol% or more. The upper limit of the content when butadiene is used is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene and isoprene are used in combination as a conjugated diene compound, an alicyclic skeleton having a combination of the substituents (ii), (iii), (v), and (vi) in the polymer block (B). When one or more kinds of (X') are present, the total content thereof is 1 mol% or more to exhibit a more excellent anti-vibration effect and suppress a decrease in adhesive strength even at a high temperature. From the viewpoint of facilitation, it is preferably 2 mol% or more, more preferably 5 mol% or more, further preferably 8 mol% or more, and further preferably 13 mol% or more. preferable. The upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X).
Further, when butadiene and isoprene are used in combination as a conjugated diene compound, one alicyclic skeleton (X) having a combination of the substituents (i) to (vi) described above is contained in the polymer block (B). When the above is present, the total content thereof is preferably 1 mol% or more from the viewpoint of exhibiting a more excellent anti-vibration effect and easily suppressing a decrease in adhesive strength even at high temperatures. It is more preferably mol% or more. The upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X).

The content of the alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product was determined by ¹³ C-NMR measurement of the block copolymer. It is a value obtained from the integrated value derived from the alicyclic skeleton (X) in B), and more specifically, it is a value measured according to the method described in Examples.

Further, the block copolymer or its hydrogenated product contains a vinyl group and a main chain bonded to the alicyclic skeleton (X) when the hydrogenation rate of the polymer block (B) is 0 mol% or more and less than 50 mol%. It is possible to specify the molar content ratio with the vinyl group bonded to.
For example, in the alicyclic skeleton (X') having a combination of the substituents (ii), (iii), (v), and (vi), the vinyl group terminal bonded to the alicyclic skeleton (X'). The chemical shift of the carbon atom ((a) of the following chemical formula) in ¹³ C-NMR appears in the vicinity of 107 to 110 ppm, and the ¹³ C of the carbon atom at the terminal of the vinyl group bonded to the main chain ((b) of the following chemical formula). -Chemical shift in NMR appears around 110-116 ppm. When the hydrogenation rate is 0 to 40 mol%, the peak area ratio [peak area of chemical shift value 107 to 110 ppm] / [peak area of chemical shift value 110 to 116 ppm] measured by ¹³ C-NMR is usually The area ratio is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, still more preferably, from the viewpoint of being in the range of 0.01 to 3.00 and exhibiting more excellent vibration damping properties. Is 0.01 to 0.50, more preferably 0.01 to 0.20.

Also, the hydrogenated product, ¹³ but ^C-NMR peaks derived from the carbon atom on the alicyclic skeleton (X) in the measurement is hardly observed, the substituent R ³ is a hydrocarbon group having 1 to 11 carbon atoms Yes, a peak derived from a carbon atom on the alicyclic skeleton (X) that binds to a branched alkyl group derived from a vinyl group having R ³ can be observed.
Accordingly, when the hydrogenation rate of the polymer block for hydrogenated product (B) is 50 to 99 mol%, alicyclic skeleton (X) above that bind to a branched alkyl group derived from a vinyl group having the R ³ It is also possible to specify the molar ratio of the carbon atom contained in the carbon atom to the carbon atom 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 atom on the alicyclic skeleton (X) bonded to the isoprene group ((c) of the following chemical formula). It appears in the chemical shift around 50.0 ~ 52.0ppm in ¹³ C-NMR of ¹³ chemical shift in C-NMR of the carbon atoms on the main chain bonded isoprene group (the following chemical formula (d)) is It appears around 43.0-45.0 ppm. When the hydrogenation rate is 40 to 99 mol%, the peak area ratio measured by ¹³ C-NMR [peak area of chemical shift value 50.0 to 52.0 ppm] / [chemical shift value 43.0 to 45]. The peak area of .0 ppm is usually in the range of 0.01 to 3.00, and the area ratio is preferably in the range of 0.01 to 1.50, more preferably from the viewpoint of exhibiting better vibration damping properties. The range is 0.01 to 1.00, more preferably 0.01 to 0.50, and even more preferably 0.01 to 0.25.
The 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 blocks (B) contained in the block copolymer is preferably from 15,000 to 15,000 in the state before hydrogenation from the viewpoint of vibration damping and handleability of the adhesive composition. It is 800,000, more preferably 50,000 to 700,000, still more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, most preferably 130,000 to 450, It is 000.

(Other structural units)
The polymer block (B) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound as long as it does not interfere with the object and effect of the present invention. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (B) is preferably less than 50 mol%, more preferably less than 30 mol%, and further. It is preferably less than 20 mol%, more preferably less than 10 mol%, and particularly preferably 0 mol%.
Examples of the other polymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and N. -Aromatic vinyl compounds such as vinylcarbazole, vinylnaphthalene and vinylanthracene, as well as methyl methacrylate, methylvinyl ether, β-pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran, 1,3- At least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadien and the like is preferably mentioned.
The block copolymer may have at least one of the above-mentioned polymer blocks (B). When 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 for producing a block copolymer, for example, a polymer block having a structural unit containing the alicyclic skeleton (X) in a main chain by polymerizing one or more kinds of conjugated diene compounds as monomers by an anionic polymerization method. (B) is formed, the monomer of the polymer block (A) is added, and if necessary, the monomer of the polymer block (A) and the conjugated diene compound are sequentially added to obtain a block copolymer. be able to.
As a method for producing an alicyclic skeleton by the above anion polymerization method, a known technique can be used (see, for example, US Pat. No. 3,966691). The alicyclic skeleton is formed at the end of the polymer due to the depletion of the monomer, and the polymerization can be restarted from the alicyclic skeleton by sequentially adding the monomer to the terminal. Therefore, the presence or absence of formation of the alicyclic skeleton and its content can be adjusted by the sequential addition time of the monomers, the polymerization temperature, the type and addition amount of the catalyst, the combination of the monomer and the catalyst, and the like. Further, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and if necessary, a Lewis base can be used.

Examples of the organolithium compound that can be used as a polymerization initiator for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of the dilithium compound that can be used as the polymerization initiator include naphthalenedilithium and dilithiohexylbenzene.
Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate and the like.
The amount of these polymerization initiators and coupling agents used is appropriately determined by the desired weight average molecular weight of the block copolymer and its hydrogenated product. Usually, the initiator such as an alkyllithium compound or a dilithium compound is 0.01 to 0.2 parts by mass per 100 parts by mass of the monomer of the polymer block (A) used for polymerization and the monomer such as a conjugated diene compound. 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 monomers.

The solvent is not particularly limited as long as it does not adversely affect the anion polymerization reaction. For example, aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene. And so on. 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.

Further, by a method of adding a Lewis base as a co-catalyst at the time of polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B), 3,4-bonds and 1,2 -The content of the bond can be increased.
Examples of Lewis bases that can be used include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane (DTHP); ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc. Glycol ethers such as tetraethylene glycol dimethyl ether; amines such as triethylamine, N, N, N', N'-tetramethylenediamine, N, N, N', N'-tetramethylethylenediamine (TMEDA), N-methylmorpholin. Classes: sodium or potassium salts of aliphatic alcohols such as sodium t-butylate, sodium t-amylate or sodium isopentylate, or dialkyl sodium cyclohexanolate, eg, sodium alicyclic alcohols such as sodium mentrate or Metal salts such as potassium salts; and the like. These Lewis bases can be used alone or in combination of two or more.

The amount of the Lewis base added includes how much the content of the alicyclic skeleton (X) is controlled, and the structural unit in which the polymer block (B) is particularly derived from isoprene and / or butadiene. In the case, it is determined by how much the vinyl bond amount of the isoprene unit and / or the butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of Lewis base added is not strictly limited, but is usually 0.1 to 1,000 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. It is preferably used in the range of 1 to 100 mol.

The average feed rate of the conjugated diene compound (hereinafter, may be referred to as “average diene feed rate”) is 150 kg / h or less per mol of the active terminal from the viewpoint of increasing the content of the alicyclic skeleton (X). Is preferable, 110 kg / h or less is more preferable, 55 kg / h or less is further preferable, 45 kg / h or less, 30 kg / h or less, or 22 kg / h or less. From the viewpoint of increasing productivity, the lower limit is preferably 1 kg / h or more, more preferably 3 kg / h or more, further preferably 5 kg / h or more, and may be 7 kg / h or more per mole of the active terminal. It may be 10 kg / h or more, or 15 kg / h or more.

After the polymerization is carried out by the above method, a block copolymer can be obtained by adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization reaction.

(Hydrogenated food)
When the block copolymer obtained by the above production method is used as a hydrogenated additive, a hydrogenation reaction (hydrogenation reaction) is carried out in the presence of a hydrogenation catalyst in an inert organic solvent. By 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, and the block copolymer can be hydrogenated.
In the hydrogenation reaction, the hydrogen pressure is about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, and the reaction temperature is about 20 to 250 ° C., preferably 50 to 180 ° C., more preferably. Can be carried out at 70 to 180 ° C. and a reaction time of usually about 0.1 to 100 hours, preferably 1 to 50 hours.
Examples of the hydrogenation catalyst include Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a single substance such as carbon, alumina, or diatomaceous earth; a transition metal compound, an alkylaluminum compound, or an alkyllithium. A transition metal catalyst composed of a combination with a compound or the like; a metallocene catalyst or the like can be mentioned.

The hydrogenated product thus obtained is coagulated by pouring the polymerization reaction solution into methanol or the like and then heated or dried under reduced pressure, or the polymerization reaction solution is poured into hot water together with steam and the solvent is azeotropically heated. It can be obtained by subjecting it to so-called steam stripping, which is then removed by heating, or by drying under reduced pressure.

Whether to use the block copolymer or the hydrogenated additive can be specified according to the performance desired in various uses of the adhesive composition. Similarly, the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) when it is used as a hydrogenation agent depends on the performance desired in various uses of the adhesive composition. Can be specified according to.
For example, the higher the hydrogenation rate of the hydrogenated product, the more the hydrogenated product can be obtained with improved heat resistance and weather resistance. The hydrogenation rate can be, 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, and 80 mol% or more and 99 mol% or less.

Therefore, it may be a block copolymer or a hydrogenated product thereof in which the hydrogenation rate of the polymer block (B) is 0 mol% or more (that is, including the case of unhydrogenation) and less than 50 mol%. Further, the polymer block (B) may be a hydrogenated product having a hydrogenation rate of 50 to 99 mol%.
The hydrogenation rate is the content of carbon-carbon double bonds in the conjugated diene compound in the polymer block (B) and the structural unit derived from the alicyclic skeleton (X), which is ¹ H after hydrogenation. -It is a value obtained by NMR measurement, and more specifically, it is a value measured according to the method described in Examples.

(Combination mode of polymer block (A) and polymer block (B))
As long as the polymer block (A) and the polymer block (B) are bonded to each other, the block copolymer is not limited in its bonding form, and is linear, branched, radial, or two of these. Any of the above-mentioned combined modes may be used. Above all, the bonding form of the polymer block (A) and the polymer block (B) is preferably linear, and as an example, the polymer block (A) is A and the polymer block (B) is. When represented by B, the diblock copolymer represented by AB, the triblock copolymer represented by ABA or BAB, and the tetra represented by ABAB. Block copolymer, pentablock copolymer represented by ABABA or BABAB, (AB) nZ type copolymer (Z is the coupling agent residue) A group is represented, and n represents an integer of 3 or more) and the like. Of these, linear triblock copolymers or diblock copolymers are preferable, and ABA type triblock copolymers are preferably used from the viewpoints of flexibility, ease of production, and the like.
Specific examples of the ABA type triblock copolymer include a styrene-butadiene / isoprene-styrene copolymer. Above all, it is preferable that the adhesive composition contains at least a styrene-hydrogenated butadiene / isoprene-styrene copolymer as a hydrogenated additive of the block copolymer.

Here, in the present specification, when the same type of polymer blocks are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as one polymer block. Is done. In accordance with this, the polymer block, which should be strictly described as YZZ (Z represents a coupling residue), including the above examples, needs to be particularly distinguished from the single polymer block Y. Except in some cases, it is displayed as Y as a whole. In the present specification, since this type of polymer block containing the coupling agent residue is treated as described above, for example, it contains the coupling agent residue and is strictly ABZBA ( The block copolymer that should be described as (Z represents a coupling agent residue) is described as ABA and is treated as an example of a triblock copolymer.

(Contents of polymer blocks (A) and (B))
The block copolymer may contain a polymerization block composed of a monomer other than the polymerization blocks (A) and (B) as long as it does not interfere with the object and effect of the present invention. The total content of the polymer block (A) and the polymer block (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is particularly preferred. If it is 90% by mass or more, it is possible to obtain a viscous adhesive composition having better vibration damping properties and easily suppressing a decrease in viscous adhesive force even at a high temperature.

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

[Tanδ]
(Peak top temperature and intensity of tan δ)
tan δ (tangent loss) is the ratio of loss elastic modulus / storage elastic modulus at a frequency of 1 Hz in dynamic viscous bullet measurement, and the peak top temperature and intensity of tan δ greatly contribute to vibration damping and other physical properties. Here, the peak top intensity of tan δ is the value of tan δ when the peak of tan δ is maximized. The peak top temperature of tan δ is the temperature at which the peak of tan δ is maximized.

In the present specification, the peak top temperature and intensity of tan δ of the block copolymer or its hydrogenated product are such that the block copolymer or its hydrogenated product is pressurized at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to obtain a thickness of 1. A 0.0 mm single-layer sheet is prepared, the single-layer sheet is cut into a disk shape, and this is measured as a test piece. The measurement conditions are, in accordance with JIS K 7244-10 (2005), 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.
The peak top temperature and tan δ intensity of the block copolymer or its hydrogenated product are more specifically measured values according to the method described in Examples.

The block copolymer or its hydrogenated product can have a peak top intensity of tan δ of 1.0 or more according to the above measurement. Some of the higher ones are 1.5 or more, and even 1.9 or more. The higher the peak top strength of tan δ, the better the physical properties such as vibration damping at that temperature, and if it is 1.0 or more, sufficient vibration damping can be obtained in an actual use environment.
Further, the block copolymer or its hydrogenated additive has a peak top temperature of tan δ of preferably −50 ° C. or higher, more preferably −40 ° C. or higher, still more preferably −30 ° C. or higher, and even more preferably −25 ° C. It is the above, and it may be 0 degreeC or more. The upper limit of the peak top temperature of tan δ may be 50 ° C. or lower, 40 ° C. or lower, or 35 ° C. or lower as long as the effect of the present invention is not impaired. Good. The range of the peak top temperature of tan δ is, for example, preferably -50 to 50 ° C, more preferably -40 to 40 ° C, still more preferably -30 to 30 ° C, and even more preferably -25 to 25 ° C. .. When the peak top temperature of tan δ is −50 ° C. or higher, sufficient vibration damping property can be obtained in an actual use environment, and when it is 50 ° C. or lower, the adhesive composition exhibits desirable adhesiveness. be able to.

(Maximum width of temperature range where tan δ is 1.0 or more)
Further, the block copolymer or its hydrogenated product has a series of temperature ranges in which tan δ at −70 to 100 ° C. measured under the above measurement conditions is 1.0 or more, and the maximum width of the temperature range is preferably 1.0. It is 12 ° C. or higher, more preferably 13 ° C. or higher, still more preferably 15 ° C. or higher, and even more preferably 17 ° C. or higher.
As described above, in the structural unit of the polymer block (B), the alicyclic skeleton (X) is incorporated in the main chain, and since it can have a higher vinyl bond amount, the molecular motion becomes smaller, so that the glass The transition temperature rises, and the glass transition becomes gentle with respect to temperature changes. As a result, the temperature range in which the tan δ of the block copolymer or its hydrogenated product is 1 or more becomes wide, and it becomes possible to exhibit vibration damping properties in a wide temperature range. When the maximum width of the temperature region in which tan δ is 1.0 or more is 12 ° C. or higher, and further, 13 ° C. or higher, better vibration damping properties can be obtained in an actual use environment. Further, the maximum width of the temperature region has no particular upper limit, but for example, from the viewpoint of productivity, the upper limit may be 35 ° C, 30 ° C, or 25 ° C. May be good.

[Adhesive-imparting resin]
The adhesive composition may contain an adhesive resin from the viewpoint of enhancing handleability and adhesive strength.
Examples of the tackifying resin include kumaron resins such as kumaron / inden resin; phenol-based resins such as pt-butylphenol / acetylene resin, phenol / formaldehyde resin, terpen / phenol resin, polyterpene resin, xylene / formaldehyde resin, and terpen-based resins. Resin: Petroleum resin such as aromatic petroleum resin, aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, modified alicyclic petroleum resin; rosin pentaerythritol ester, rosin glycerol ester, etc. Rosin-based resins such as rosin esters, hydrogenated rosins, methyl esters of hydrogenated rosins, pentaerythritol esters of polymerized rosins, hydrogenated rosin esters, refractory rosin-based resins, polymerized rosins, cured rosins, and special rosin esters. And so on. Among them, an alicyclic saturated hydrocarbon resin can be preferably used as the tackifier resin. Examples of the alicyclic saturated hydrocarbon resin include those obtained by hydrogenating an aromatic petroleum resin, and for example, a commercially available product such as the “Arcon” series manufactured by Arakawa Chemical Industry Co., Ltd. may be used. These tackifier resins may be used alone or in combination of two or more.
Further, in the case of applications where it is preferable to reduce the adhesive residue of the obtained adhesive composition, improve heat resistance and weather resistance, and avoid coloring the sealant or the like, it is preferable to use a hydrogenated tackifier resin.
The softening point of the tackifier resin is preferably 85 to 160 ° C, more preferably 90 to 150 ° C, and even more preferably 95 to 145 ° C. When the softening point of the tackifier resin is 85 ° C. or higher, it becomes easy to suppress a decrease in the adhesive holding power at a high temperature (about 60 ° C.), and when it is 160 ° C. or lower, the handleability of the adhesive composition is good. ..

[Plasticizer]
The adhesive composition may contain a plasticizer from the viewpoint of exhibiting flexibility and facilitating imparting adhesiveness.
Examples of the plasticizer include paraffin-based, naphthen-based, and aromatic process oils; phthalic acid derivatives such as dioctylphthalate and dibutylphthalate; white oil; mineral oils; liquid copolymers of ethylene and α-olefins; liquid paraffins; Polybutene; low molecular weight polyisobutylene; liquid polydiene such as liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, and hydrogenated products thereof. Be done. Among them, from the viewpoint of compatibility with block copolymers and their hydrogenated products, paraffin-based process oils; liquid co-oligomers of ethylene and α-olefins; liquid paraffins; low molecular weight polyisobutylene; and hydrogenated products thereof. Is preferable, and hydrogenated paraffin-based process oil is more preferable. These plasticizers may be used alone or in combination of two or more.

[filler]
The adhesive composition may contain a filler depending on the properties required for various uses.
Examples of the filler include talc, mica, calcium silicate, glass, glass flakes, glass beads, hollow spheres of glass, glass fibers, calcium carbonate, magnesium carbonate, zinc carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide. , Calcium hydroxide, zinc borate, dosonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, silica alumina, diatomaceous soil, wollastonite, zeolite, boehmite, sodium aluminosilicate, magnesium silicate, graphene, barium carbonate , Silicon nitride, aluminum hydroxide, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), magnesium silicate (atapulsite), aluminum borate, calcium sulfate, magnesium sulfate, alumina, titanium oxide , Iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, carbon nanotubes, graphite, carbon fiber, activated charcoal, hollow spheres of carbon, calcium titanate, lead zirconate titanate, carbonized Inorganic fillers such as silicon; organic fillers such as wood powder and starch; organic pigments and the like can be mentioned. These fillers may be used alone or in combination of two or more.

[Content]
In the present embodiment, the adhesive composition is at least one selected from 1 to 1000 parts by mass of a tackifier resin and 1 to 1000 parts by mass of a plasticizer with respect to 100 parts by mass of a block copolymer or a hydrogenated product thereof. including. The tackifier resin and the plasticizer may contain either one or both depending on the use of the adhesive composition.
If the content of the tackifier resin is less than 1 part by mass, the performance of the tackifier resin cannot be imparted to the adhesive composition, and if it exceeds 1000 parts by mass, the adhesive strength at low temperature may decrease. There is. Further, if the 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 exceeds 1000 parts by mass, the adhesive force at high temperature may decrease. There is.

From the viewpoint of easily maintaining the adhesive strength even at high temperatures, the content of the tackifier resin is preferably 120 to 1000 parts by mass with respect to 100 parts by mass of the block copolymer or its hydrogenated additive. Further, from the viewpoint that good handleability of the adhesive composition is easily exhibited and it is easy to maintain a better adhesive force, the block copolymer or its hydrogenated product adheres to 100 parts by mass. The content of the imparting resin is more preferably 130 parts by mass or more, still more preferably 140 parts by mass or more. On the other hand, from the viewpoint of adhesive strength at low temperature, the content of the tackifier resin is more preferably 900 parts by mass or less, still more preferably 700 parts by mass, based on 100 parts by mass of the block copolymer or its hydrogenated additive. It is less than or equal to parts by mass, 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 with respect to 100 parts by mass of the block copolymer or its hydrogenated product. Further, from the viewpoint of improving the handleability and flexibility of the adhesive composition, the content of the plasticizer is more preferably 70 parts by mass or more with respect to 100 parts by mass of the block copolymer or its hydrogenated product. More preferably, it is 80 parts by mass or more. On the other hand, from the viewpoint of appropriate flexibility and adhesive strength, the content of the plasticizer is more preferably 900 parts by mass or less, more preferably 900 parts by mass or less, based on 100 parts by mass of the block copolymer or its hydrogenated additive. It is 700 parts by mass or less, more preferably 400 parts by mass or less.

Further, in the present 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 use of the adhesive composition.
From the viewpoint of preferably exhibiting the flexibility and vibration damping property of the adhesive composition, the content of the filler is preferably 10 to 2500% by mass with respect to 100 parts by mass of the block copolymer or its hydrogenated material. It is a department. Further, from the viewpoint of improving the handleability 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. More preferably, it is 20 parts by mass or more. On the other hand, from the viewpoint of excellent vibration damping and easy maintenance of adhesiveness even at high temperatures, the content of the filler is more preferably 2400 with respect to 100 parts by mass of the block copolymer or its hydrogenated material. It is less than or equal to parts by mass, more preferably 2200 parts by mass or less.

The total content of the block copolymer or its hydrogen additive in the adhesive composition, at least one selected from the tackifier resin and the plasticizer, and the filler is preferably 80% by mass or more, more preferably. It is 85% by mass or more, more preferably 90% by mass or more.

Further, in the present embodiment, the content of each component can specify a suitable range depending on the use of the adhesive composition. An example of the content of the adhesive composition according to the intended use is shown below, but the content is not limited thereto.
(Surface protection film)
When the adhesive composition is used for the adhesive layer in a surface protective film including an adhesive layer, the content of the adhesive resin is appropriate adhesion to 100 parts by mass of the block copolymer or its hydrogenated material. From the viewpoint of the balance between the adhesive force and the small amount of adhesive residue, it is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and further preferably 10 to 70 parts by mass.
In the same case as above, the content of the plasticizer is preferably 0 to 100 parts by mass, more preferably from the viewpoint of the balance between bleeding suppression and adhesive strength, with respect to 100 parts by mass of the block copolymer or its hydrogenated product. Is 0 to 90 parts by mass, more preferably 0 to 80 parts by mass.

(Hot melt adhesive)
When the adhesive composition is used as a hot melt adhesive, the content of the tackifying resin is based on the adhesive strength at normal temperature to high temperature and the adhesive strength at low temperature with respect to 100 parts by mass of the block copolymer or its hydrogenated product. From the viewpoint of the balance of adhesive force, the amount is preferably 30 to 1000 parts by mass, more preferably 50 to 700 parts by mass, and further preferably 100 to 500 parts by mass.
In the same case as above, the content of the plasticizer with respect to 100 parts by mass of the block copolymer or its hydrogenated product is preferably from the viewpoint of the balance between the adhesive force at low temperature and the holding power at room temperature to high temperature. It is 0 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 25 to 300 parts by mass.

[Additive]
The adhesive composition may contain various additives in addition to the above-mentioned block copolymer and its hydrogenated additive, tackifier resin, plasticizer, and filler as long as the effects of the present invention are not impaired. it can.
Examples of the additive include a cross-linking agent (isocyanate-based cross-linking agent, epoxy-based cross-linking agent, metal chelate-based cross-linking agent, aziridine-based cross-linking agent, amine resin, etc.), heat stabilizer, light stabilizer, ultraviolet absorber, infrared absorption. Agents, antioxidants, lubricants, colorants, antistatic agents, flame retardants, water repellents, waterproofing agents, hydrophilicity imparting agents, conductivity imparting agents, thermal conductivity imparting agents, electromagnetic wave shielding imparting agents, translucency Conditioning agent, fluorescent agent, slidability imparting agent, transparency imparting agent, antiblocking agent, metal inactivating agent, antibacterial agent, crystal nucleating agent, crack inhibitor, ozone deterioration inhibitor, rodent inhibitor, dispersant , Thickeners, light-resistant agents, weather-resistant agents, copper damage inhibitors, reinforcing agents, mold-proofing agents, macrocyclic molecules (cyclodextrin, calix array, cucurbituril, etc.), olefin resins, and resins other than olefin resins. it can.
Examples of the olefin resin include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylene such as homopolypropylene, block polypropylene, and random polypropylene; homopolymers or copolymers of α-olefin. Examples include polypropylene and / or a copolymer of ethylene and α-olefin. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-. Examples thereof include α-olefins having 20 or less carbon atoms such as octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or two of these. The above can be used. Further, a modified olefin resin obtained by modifying these olefin resins with maleic acid or the like can also be used.
Resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, nitrile rubber, butyl rubber, natural rubber, and ethylene-vinyl acetate copolymer. , Ethylene- (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer metal ion cross-linked resin (ionomer) ), Polystyrene resin such as polystyrene, AS resin, ABS resin, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resin, polyoxymethylene homo. Examples include polymers, acetal resins such as polyoxymethylene copolymers, acrylic resins such as polymethyl methacrylate-based resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl chloride-vinyl acetate copolymers. Be done.
The above additives can 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, the content of the additive in the adhesive composition is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less. preferable. When the content of the additive is 10% by mass or less, it is considered that the behavior of the tan δ strength described later is hardly affected.
The total content of the block copolymer or its hydrogenated additive in the adhesive composition, at least one selected from the tackifier resin and the plasticizer, and the filler is preferably 80% by mass or more, more preferably. It may be 85% by mass or more, more preferably 90% by mass or more, 95% by mass or more, or 98% by mass or more.

[Adjustment method of adhesive composition]
The method for adjusting the adhesive composition is not particularly limited, and for example, it can be adjusted using a kneading device. As the kneading device, a method generally used in this field can be adopted. Each component may be mixed by using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or after mixing, the mixture may be kneaded by a uniaxial or biaxial extruder, a kneader or the like. .. The temperature at the time of melt-kneading can be appropriately set, but is usually 150 to 300 ° C, preferably 160 to 250 ° C.
The obtained adhesive composition can be in an appropriate form depending on the intended use, usage mode, etc., and may be in the form of granules, flakes, pellets, etc., for example.
Further, the adhesive composition can be adjusted by dissolving each component in various organic solvents, mixing them, and then removing the organic solvent by drying or the like. Examples of the organic solvent include fats such as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetone, acetylacetone, cyclohexanone, heptane, isopentan, n-hexane and cyclohexane. Examples thereof include group solvents, aromatic solvents such as benzene, toluene and ethyl benzene.

≪Physical properties of adhesive composition≫
[Tanδ strength]
The above-mentioned block copolymer or hydrogenated product thereof can exhibit excellent vibration damping properties. Therefore, the adhesive composition containing the block copolymer or its hydrogenated product has a peak top strength of tan δ of preferably 1.0 or more, more preferably 2.0 or more, and further 2.6 or more. There is also something that becomes. 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 50 ° C. or lower, and may be 40 ° C. or lower, as long as the effect of the present invention is not impaired.
Further, the tan δ strength of the adhesive composition at a temperature of 23 ° C. can be preferably 0.15 or more, more preferably 0.30 or more, still more preferably 0.50 or more. The tan δ strength of the adhesive composition at a temperature of 40 ° C. can be preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.15 or more. The tan δ strength of the adhesive composition at a temperature of 60 ° C. can be preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.15 or more.

[Storage modulus]
In the present embodiment, the ratio of the shear storage elastic modulus G'(23 ° C.) to the shear storage elastic modulus G'(60 ° C.) [G'(23 ° C.) / G'(60 ° C.)] is preferable. Is 1.3 or higher.
In the present embodiment, the adhesive composition contains the above-mentioned block copolymer or a hydrogenated product thereof, so that the ratio of the storage elasticity [G'(23 ° C.) / G'(60 ° C.)] is increased. It becomes easier to achieve 1.3 or higher. Generally, the adhesive strength decreases as the temperature rises, but in the present embodiment, if the ratio of storage elastic modulus [G'(23 ° C) / G'(60 ° C)] is 1.3 or more, 23 The degree of decrease in peel strength from ° C. to 60 ° C. becomes small, and the peeling tends to be difficult even at high temperatures.
In the present embodiment, the ratio of storage elastic modulus [G'(23 ° C.) / G'(60 ° C.)] is the adhesive composition (the above-mentioned block copolymer or its hydrogenated product, the above-mentioned adhesion. By adjusting the type and content of the resin coating, the above-mentioned plasticizer, and the above-mentioned filler and optional components), the ratio can be 1.5 or more, further 1.7 or more.
The shear storage elastic modulus is a value measured in more detail according to the method described in Examples.

[Peeling strength]
In the present embodiment, the peel strength of the adhesive composition is preferably 180 degrees peel strength measured in accordance with JIS Z 0237 (2009) using an acrylic resin plate as an adherend at a measurement temperature of 23 ° C. It can be 10.0 N / 25 mm or more, more preferably 15.0 N / 25 mm or more, still more preferably 20.0 N / 25.0 mm or more, still more preferably 25.0 N / 25.0 mm or more. Further, the peel strength under the same conditions is preferably 5.0 N / 25 mm or more, more preferably 8.0 N / 25 mm or more, still more preferably 11.0 N / 25 mm or more, still more preferably 12.0 N at a measurement temperature of 60 ° C. It can be / 25 mm or more, particularly preferably 14.0 N / 25 mm or more. Generally, the adhesive strength decreases as the temperature rises, but in the present embodiment, the above-mentioned block copolymer or its hydrogenated additive is contained, and the content thereof is adjusted to a suitable range to adjust the adhesive strength. Will be easier to achieve.
Further, in the present embodiment, the ratio of the peel strength at 60 ° C. to the peel strength at 23 ° C. of the adhesive composition is 0.2 or more, further 0.3 or more, and further 0.4 or more. It is also possible to. The ratio of the peel strength is the composition of the adhesive composition (the above-mentioned block copolymer or its hydrogenated additive, the above-mentioned adhesive resin, the above-mentioned plasticizer, and the above-mentioned filler and the type of optional component. It becomes easier to achieve by adjusting the content) and the like.
The peel strength is a value measured in more detail according to the method described in Examples.

≪Use≫
It can be a pressure-sensitive adhesive containing the above-mentioned pressure-sensitive adhesive composition.
The adhesive may be used after being heated and melted, for example. Further, the adhesive can be used as a solution adhesive by using, for example, various organic solvents and dissolving the adhesive so that the solid content concentration is about 5 to 70% by mass. Examples of the organic solvent include fats such as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetone, acetylacetone, cyclohexanone, heptane, isopentan, n-hexane and cyclohexane. Examples thereof include group solvents, aromatic solvents such as benzene, toluene and ethyl benzene.
Further, it can be used as a hot melt adhesive containing an adhesive composition, for example, a block copolymer or a hydrogenated product thereof, an adhesive resin, and if necessary, a plasticizer. The material is suitable for hot melt adhesives.

[Sealant]
It can be a sealant containing the above-mentioned adhesive composition.
The above-mentioned adhesive composition can be used as a sealant as it is, but cross-linking may be performed if necessary as long as the effects of the present invention are not impaired. When cross-linking, a radical generator, a cross-linking agent such as sulfur or a sulfur compound can be used. Further, when cross-linking is performed using sulfur or a sulfur compound, a vulcanization accelerator may be used as a cross-linking aid, if necessary.

Examples of the radical generator include hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide; di-t-butyl peroxide, t-butylcumyl peroxide, and dik. Milperoxide, α, α'-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Dialkyl peroxides such as di (t-butylperoxy) -hexin-3; diacyl peroxides such as acetyl peroxides, succinate peroxides and benzoyl peroxides; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy Peroxide esters such as isopropyl carbonate, organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; inorganic peroxides such as hydrogen peroxide, persulfate and metal oxides, azo compounds, mono and disulfides, metals Examples include chelate and redox initiator. When these radical generators are used, they are preferably in the range of 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the block copolymer or its hydrogenated product. used.

Examples of the sulfur compound include sulfur monochloride and sulfur dichloride.
When sulfur or a sulfur compound is used, the content of sulfur or sulfur compound in the adhesive composition is preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the block copolymer or its hydrogenated product. It is preferably 0.2 to 10 parts by mass.

Examples of the vulcanization accelerator include thiazoles such as N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, and 2- (4-morpholinodithio) benzothiazole; diphenylguanidine and triphenylguanidine. Guanidins such as; aldehyde-amine-based reactants such as butylaldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants or aldehyde-ammonia-based reactants, imidazolines such as 2-mercaptoimidazolin; Thioureas such as thiourea, trimethylthiourea, diorsotrilthiourea; thiuram mono or polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, pentamethylene thiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, dimethyl Thiocarbamates such as sodium dithiocarbamate, selenium dimethyldithiocarbamate, telluryl diethyldithiocarbamate; xanthogenates such as zinc dibutylxanthogenate, organic peroxides, zinc flower and the like can be mentioned. These vulcanization accelerators may be used alone or in combination of two or more. 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 with respect to 100 parts by mass of the block copolymer or its hydrogenated product. , More preferably 0.2 to 10 parts by mass.

In the case of a sealant, the adhesive composition preferably contains at least one selected from the above-mentioned fillers and additives.
When the sealant is used, it is preferable to use a filler from the viewpoint of vibration damping. Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate, glass fiber, and carbon fiber.
When a filler is contained to prepare a sealant, the content of the filler in the adhesive composition is preferably 10 to 200 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the block copolymer or its hydrogenated product. Is 10 to 150 parts by mass.
Further, among the additives, it is preferable to use a lubricant from the viewpoint of improving the fluidity of the sealant and suppressing thermal deterioration. Examples of the lubricant include silicon oil; hydrocarbon-based lubricants such as paraffin wax, microwax and polyethylene wax; butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, and stearyl stearate.
When a lubricant is contained to prepare a sealant, the content of the lubricant in the adhesive composition is preferably 1 to 20 parts by mass, more preferably 1 with respect to 100 parts by mass of the block copolymer or its hydrogenated product. ~ 15 parts by mass.

[Other]
In this embodiment, the adhesive adhesive and the hot melt adhesive containing the adhesive composition can be used for various purposes.
Adhesives and hot melt adhesives include, for example, disposable diapers, adult incontinence products, sanitary napkins, bed pads, first aid bonds, surgical drapes, single-sided tape, double-sided tape, transfer tape, labels, plastic sheets, non-woven fabrics. Use with sheets, paper sheets, cardboard, books, filters, or articles with packaging;
Use in gasket sealants (especially in the fields of automobiles, electrical parts, technical lighting);
Use in the manufacture of resealable trays of multilayer films;
Use in articles containing materials for mailing containers;
Anti-vibration material, cushioning material, shock absorber, low-resilience material, fall-prevention material, seismic isolation material, seismic isolation material, or vibration-damping material (preferably sound deadening material, more preferably damping or sound deadening material mat, pad in the automobile industry. , Sheets and tapes);
Use in electronic devices (especially LCD displays, LED displays, touch screens, or flexible thin film solar cells);
Use in percutaneous drug delivery systems;
Couplings between pipes (preferably cooling coils), electronic components (preferably light emitting elements, computer equipment, mobile phones, tablets, touch screens, automotive technology hi-fi systems, and audio systems), solar-heated thermal pipes and water tanks. Department, fuel cell and wind turbine, computer chip manufacturing, optical device, battery, housing, cooler, heat exchange device, wire, cable, heating wire, refrigerator, dishwasher, air conditioner, accumulator, transformer, laser equipment, functionality Use in clothing, car seats, medical equipment, fire protection, electric motors, planes, and trains;
Use in filaments of 3D printing materials, injection sealants or molding sealants to seal heat-generating devices;
Use for joining articles with substrates made of wood, metal, polymer plastics, glass and textiles; use for joining to the outer surface in water towers; glazing in the manufacture of footwear or in the manufacture of windows Use as a compound, in the manufacture of doors and building panels, or in the manufacture of portable devices and displays;
Bookbinding, wood bonding, flat lamination, flexible packaging, profile wrapping, edge banding, textile lamination, low pressure molding, and use in shoes;
Use in the manufacture of bonded fabrics / fabrics for books, packaging films, rigid panels, furniture, windows, footwear, automobile headlights, automobile trims or garments;
Use in decorative films;
Can be mentioned.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

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

(2) Weight average molecular weight (Mw)
The polystyrene-equivalent weight average molecular weight (Mw) of the hydrogenated block copolymer was determined by gel permeation chromatography (GPC) measurement under the following conditions.
(GPC measuring device and measuring conditions)
-Device: GPC device "HLC-8020" (manufactured by Tosoh Corporation)
Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Toso Co., Ltd. were connected in series.
-Eluent: tetrahydrofuran-Eluent flow rate: 0.7 mL / min
-Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C
-Detector: Differential refractive index (RI) detector-Calibration curve: Created using standard polystyrene

(3) Hydrogenation rate in the polymer block (B) ¹ Calculated from the ratio of the peak area derived from the residual olefin of isoprene and / or butadiene to the peak area derived from ethylene, propylene and / or butylene by H-NMR measurement. ..
-Device: Nuclear magnetic resonance device "ADVANCE 400 Nano bay" (manufactured by Bruker)
-Solvent: CDCl ₃

(4) Amount of vinyl bond in polymer block (B) ¹ H-NMR measurement by dissolving the block copolymer before hydrogenation in CDCl ₃ [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature : 30 ° C.]. The total peak area of structural units derived from isoprene and / or butadiene, and 3,4-bonding units and 1,2-bonding units in isoprene structural units, 1,2-bonding units in butadiene structural units, or isoprene and butadiene. In the case of structural units derived from the mixture, the vinyl bond amount (total content of 3,4-bonding unit and 1,2-bonding unit) was calculated from the ratio of the peak areas corresponding to each of the binding units.

(5) using 10mmNMR tube block copolymer 600mg and Cr _(acac) 3 40 mg of the content water before hydrogenation of the polymer block (B) an alicyclic skeleton (X) in was dissolved in CDCl ₃ 4 mL Quantitative ¹³ C-NMR measurement (pulse program: zgig, Inverse gated 1H decoupling method) [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C.], and block the polymer by the following method. The contents of each of the alicyclic skeletons X, X1 and X2 in (B) were calculated.
In Table 3, X, X1 and X2 show the following alicyclic skeletons.
X: Alicyclic skeleton having a combination of the following (i) to (vi) substituents X1: Alicyclic skeleton having a combination of the following (i) and (iv) substituents X2: Below (ii), ( iii) Alicyclic skeleton with a combination of substituents (iv), (v), (iv): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Bd + Bd)
(Ii): R ¹ = hydrogen atom, R ² = methyl group, R ³ = hydrogen atom; (1,2Bd + 1,2Ip)
(Iii): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = methyl group; (1,2Bd + 3,4Ip)
(Iv): R ¹ = methyl group, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Ip + Bd)
(V): R ¹ = methyl group, R ² = methyl group, R ³ = hydrogen atom; (1,2Ip + 1,2Ip)
(Vi): R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group; (1,2Ip + 3,4Ip)

[Calculation method]
The structure derived from each peak is shown in Table 1-1. Assuming that the integrated values of the peaks are a to g, the integrated values of each structure are as shown in Table 1-2, and the contents of X, X1 and X2 are (a + g−c) / (a + b + cd + e /, respectively). 2 + 2f), (g-c) / (a + b + cd + e / 2 + 2f), a / (a + b + cd + e / 2 + 2f).

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

(7) Peak top temperature of tan δ, peak top strength, maximum width of temperature region where tan δ is 1.0 or more, tan δ strength at 20 ° C and 30 ° C or less Hydrogenated block copolymer for measurement Was pressurized at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to prepare a single-layer sheet having a thickness of 1.0 mm. The single-layer sheet was cut into a disk shape and used as a test sheet.
For the measurement, based on JIS K 7244-10 (2005), as a parallel plate vibration rheometer, a distortion control type dynamic viscoelastic device "ARES-G2" with a disk diameter of 8 mm (TA Instruments) Ment Japan Co., Ltd.) was used.
The test sheet completely fills the gap between the two flat plates, and with a strain amount of 0.1%, the test sheet is vibrated at a frequency of 1 Hz, and a constant temperature of 3 ° C./min is applied from −70 ° C. to 100 ° C. The temperature rose quickly. The temperature of the test sheet and the disk was maintained until there was no change in the measured values of shear loss elastic modulus and shear storage elastic modulus, and the maximum value (peak top intensity) of the peak intensity of tan δ and the maximum value were obtained. The temperature (peak top temperature) was determined. Further, the maximum width of the temperature region where tan δ is 1.0 or more, and the tan δ intensity at 20 ° C. and 30 ° C. were determined. The larger the value, the better the vibration damping property.

[Manufacturing Example 1]
Production of Hydrogen Additive (H-TPE-1) 87 g (sec) of sec-butyllithium cyclohexane solution containing 50 kg of cyclohexane as a solvent and 10.5% by mass of anionic polymerization initiator in a pressure-resistant container that has been replaced with nitrogen and dried. -Substantial addition amount of butyllithium: 9.1 g) was charged.
After raising the temperature inside the pressure-resistant container to 50 ° C., 1.0 kg of styrene (1) is added and polymerized for 1 hour. At the temperature inside the container at 50 ° C., 2,2-di (2-tetrahydrofuryl) propane (2-tetrahydrofuryl) propane as a Lewis base ( 63 g of DTHP) was added, and a mixture of 8.16 kg of isoprene and 6.48 kg of butadiene was added at the average diene feed rate shown in Table 2 over 5 hours and then polymerized for 2 hours, and 1.0 kg of styrene (2) was further added. In addition, it was polymerized for 1 hour to obtain a reaction solution containing a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer.
A Ziegler-based hydrogenation catalyst formed of nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out under the conditions of a hydrogen pressure of 1 MPa and 80 ° C. for 5 hours. After allowing the reaction solution to cool and pressurize, the catalyst is removed by washing with water and vacuum dried to obtain a hydrogenated product of a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer (hereinafter, H). -Sometimes referred to as TPE-1) was obtained.
Table 2 shows each raw material and the amount used thereof. The results of the physical property evaluation are shown in Table 3.

[Comparative Manufacturing Example 1]
Production of Hydrogenated Additive (H-TPE-1') The block copolymer was prepared in the same manner as in Production Example 1 except that the components, their amounts used, and the reaction conditions were changed as shown in Table 2. A hydrogenated product (H-TPE-1') was produced. The results of the physical property evaluation are shown in Table 3.

The block copolymer of Production Example 1 and its hydrogenated product have a peak top intensity of tan δ of 1.0 or more, and a peak top temperature of tan δ in a wide temperature range. Therefore, they are widely used as vibration damping materials. It can be said that it is suitable. In particular, as compared with Comparative Production Example 1, it can be seen that Production Example 1 has a relatively high tan δ intensity at 20 ° C. and 30 ° C., and is excellent in vibration damping properties near room temperature.

<Adhesive composition>
[Examples 1 to 5] [Comparative Examples 1 to 5]
(Method for Producing Adhesive Composition <1>)
According to the formulation shown in Table 4, the hydrogen additives (H-TPE-1, H-TPE-1') of the block copolymers obtained in Production Example 1 and Comparative Production Example 1 and the tackifier resin were used. A toluene solution was prepared by adding the same mass part of toluene to the total of the plasticizer and the antioxidant (additive). After applying this toluene solution to a polyethylene terephthalate (PET) film (trade name: Teijin Tetron Film G2, manufactured by Teijin DuPont Film Co., Ltd.) with a thickness of 50 μm using a baker-type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.). , 60 ° C. for 30 minutes to prepare a viscous adhesive composition on a PET film. The thickness of this adhesive composition was 30 μm.

(Method for Producing Adhesive Composition <2>)
After preparing a toluene solution in the same manner as in the above (method for producing an adhesive composition <1>), 5 g of this toluene solution is added to a paper box (with the release PET surface inside) having a length of 5 cm, a width of 5 cm, and a height of 3 cm. The adhesive composition was prepared by drying at 23 ° C. for 24 hours and further at 60 ° C. for 8 hours. The thickness of this adhesive composition was 1 mm.

[Example 6] [Comparative example 6]
(Method for Producing Adhesive Composition <3>)
According to the formulation shown in Table 4, the hydrogenated substances (H-TPE-1, H-TPE-1') of the block copolymers obtained in Production Example 1 and Comparative Production Example 1, the tackifier resin, and the plasticizer. The agent, filler, and antioxidant (additive) are put into Brabender (“Plastograph EC 50cc mixer” manufactured by Brabender), and melt-kneaded at a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm for 3 minutes. After that, the obtained composition was press-molded (200 ° C., 2 minutes) by inserting a polyethylene terephthalate (PET) film (trade name: Teijin Tetron Film G2, manufactured by Teijin DuPont Film Co., Ltd.) with a thickness of 50 μm on one side. By doing so, a sticky adhesive composition was prepared on the PET film. The thickness of this adhesive composition was 0.5 mm.

(Method for Producing Adhesive Composition <4>)
After melt-kneading in the same manner as in the above (method for producing an adhesive composition <3>), the obtained composition is press-molded (200 ° C., 2 minutes) to produce an adhesive composition. did. The thickness of this adhesive composition was 1 mm.

[Evaluation of the physical properties]
The physical property evaluation of the prepared adhesive composition is shown below.
(Peak top temperature of tan δ, peak top strength, shear storage elastic modulus at 23 ° C, 60 ° C, tan δ strength at 23 ° C, 40 ° C, 60 ° C, complex viscosity at 60 ° C (shear, 1 Hz))
Measurements were made according to JIS K 7244-10 (2005). Specifically, the viscoelastic composition obtained by the above (method for producing a viscoelastic composition <2>) (method for producing a viscoelastic composition <4>) is cut into a disk shape having a diameter of 8 mm. Using the distortion-controlled dynamic viscoelastic device "ARES-G2" (manufactured by TA Instruments), the sample was sandwiched between flat plates with a diameter of 8 mm, the strain amount was 0.1%, and the frequency. By applying vibration at 1 Hz and raising the temperature from -70 ° C to 180 ° C at 3 ° C / min for measurement, the peak top temperature and peak top intensity of tan δ, and the shear storage elastic modulus (G') at 23,60 ° C. , 23 ° C., 40 ° C., 60 ° C., tan δ intensity, and 60 ° C., complex viscosity were measured. The results are shown in Table 4.

(Shore A hardness)
Six sheets of the adhesive composition obtained in the above (method for producing the adhesive composition <4>) were stacked to form a test piece for hardness measurement having a thickness of 6 mm, according to JIS K 6253 (2012). Then, the shore A hardness of the adhesive composition was measured using an automatic rubber hardness tester P2-A type (manufactured by a polymer meter). The results are shown in Table 4.

(Peeling strength at 23 ° C)
On an acrylic extruded plate (trade name: Sumipex E, thickness 1.5 mm, manufactured by Sumika Acrylic Sales Co., Ltd.), (Method for producing adhesive composition <1>) (Method for producing adhesive composition <3> The adhesive composition obtained in (1) was attached so as to be in contact with the acrylic resin plate, and cut into a width of 25 mm as a test piece. From the polyethylene terephthalate side of this test piece, the test piece was compacted twice at a speed of 10 mm / min using a 2 kg rubber roller, and then left to stand for 24 hours in an atmosphere of 23 ± 1 ° C. and a humidity of 50 ± 5%. Then, 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 increased at a peeling rate of 300 mm / min. It was measured and used as the peel strength at 23 ° C. The results are shown in Table 4.

(Peeling strength at 60 ° C)
After leaving for 24 hours in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 5%, leaving for 10 minutes in an atmosphere of 60 ° C., and then measuring the peel strength in an atmosphere of 60 ° C., the above (peeling strength at 23 ° C.) ), The peel strength was set at 60 ° C. The results are shown in Table 4.

Each component shown in Table 4 is as follows.
-Adhesion-imparting resin (1): Alcon P-100 (alicyclic saturated hydrocarbon resin, softening point (ring ball method) 100 ± 5 ° C., manufactured by Arakawa Chemical Industries, Ltd.)
-Adhesion-imparting resin (2): Archon P-125 (alicyclic saturated hydrocarbon resin, softening point (ring ball method) 125 ± 5 ° C, manufactured by Arakawa Chemical Industries, Ltd.)
-Plasticizer: Diana process oil PW-90 (hydrogenated paraffin-based process oil, manufactured by Idemitsu Kosan Co., Ltd.)
・ Filler: Escalon # 200 (heavy calcium carbonate, manufactured by Sankyo Seiko Co., Ltd.)
-Antioxidant: ADEKA STAB AO-60 (Hindered phenolic antioxidant, manufactured by ADEKA CORPORATION)

From Table 4, the adhesive composition of Examples 1 to 6 has a larger value of the peak top strength of tan δ than the adhesive composition of Comparative Examples 1 to 6, and tan δ in the temperature range of 23 to 60 ° C. The strength value is large.
In addition, the adhesive compositions of Examples 1 to 6 have a lower complex viscosity at 60 ° C. than the adhesive compositions of Comparative Examples 1 to 6.
Further, the cohesive adhesive compositions of Examples 1 to 6 have a storage elastic modulus G'ratio [G'(23 ° C.) / G'(60 ° C.)) as compared with the cohesive adhesive compositions of Comparative Examples 1 to 6. ] Is large, 1.5 or more. As described above, in the adhesive composition of the example, the ratio of the storage elastic modulus of 23 ° C. and 60 ° C. was larger than that of the comparative example, and the decrease in peel strength from 23 ° C. to 60 ° C. was small [(60). (Peeling strength at ° C) / (Peeling strength at 23 ° C) is large].
Therefore, the viscous adhesive composition of the example contains a block copolymer having a structural unit containing an alicyclic skeleton (X) in the main chain or a hydrogenated additive thereof, thereby excellent vibration damping and handling. It can be seen that it has properties and adhesive strength, and that adhesiveness is maintained even under high temperature conditions.

Although it is not certain, the adhesive composition containing the block copolymer or its hydrogenated material is softened at a high temperature (60 ° C.), so that the surface of the adherend (acrylic resin plate) has minute irregularities. The convex part of the surface of the adhesive composition that permeates into the material and acts like an anchor, or the convex part of the surface of the adhesive composition that comes into contact with the adherend bites into the concave part of the adherend, and an elastic tightening force acts. It is presumed that the decrease in the adhesive force between the adhesive composition and the adherend was suppressed.
Further, the adhesive composition of Example 6 has a low shore A hardness. Therefore, the adhesive composition of the example containing the filler is excellent as a sealant by containing a block copolymer having a structural unit containing an alicyclic skeleton (X) in the main chain or a hydrogenated product thereof. It can be seen that it has vibration damping properties, handleability, flexibility and adhesive strength, and that the adhesive properties are maintained even under high temperature conditions.

The adhesive composition of the present invention has vibration damping properties and has adhesive properties that are difficult to peel off even at high temperatures, and is therefore useful as an adhesive, particularly a hot melt adhesive. The adhesive composition of the present invention can also be used as a sealant.

Claims (20)

1. A viscous adhesive composition containing at least one selected from 1 to 1000 parts by mass of a tackifier resin and 1 to 1000 parts by mass of a plasticizer with respect to 100 parts by mass of the following block copolymer or hydrogenated product thereof.
   The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.
   

   

   (In the above formula (X), R ¹ to R ³ 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.)
2. The adhesive composition according to claim 1, which contains 120 to 1000 parts by mass of the tackifying resin.
3. The adhesive composition according to claim 1 or 2, which contains 60 to 1000 parts by mass of the plasticizer.
4. The adhesive composition according to any one of claims 1 to 3, further comprising 10 to 2500 parts by mass of a filler.
5. The alicyclic skeleton (X) includes the alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a hydrocarbon group having 1 to 11 carbon atoms, according to claims 1 to 4. The viscous adhesive composition according to any one.
6. The adhesive composition according to claim 5, wherein the hydrocarbon group in the alicyclic skeleton (X') is a methyl group.
7. The adhesive composition according to any one of claims 1 to 6, which contains at least a styrene-hydrogenated butadiene / isoprene-styrene copolymer as a hydrogenated additive of the block copolymer.
8. The adhesive composition according to any one of claims 1 to 4, wherein R ¹ to R ³ are hydrogen atoms at the same time.
9. The adhesive composition according to any one of claims 1 to 8, wherein the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X).
10. The adhesive composition according to claim 5 or 6, wherein the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X').
11. 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%.
12. 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%.
13. The adhesive composition according to any one of claims 1 to 12, wherein the amount of vinyl bond in the polymer block (B) is 55 to 95 mol%.
14. The block copolymer or its hydrogenated product conforms to JIS K 7244-10 (2005), has a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to 100 ° C., and a temperature rise rate of 3 ° C./ The adhesive composition according to any one of claims 1 to 13, wherein there is a series of temperature regions in which tan δ measured under the condition of minutes is 1.0 or more, and the maximum width of the temperature region is 13 ° C. or more. Stuff.
15. The adhesive composition according to any one of claims 1 to 14, wherein the polymer block (A) contains more than 70 mol% of structural units derived from an aromatic vinyl compound.
16. 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.
17. 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.
18. The ratio of the shear storage elastic modulus G'(23 ° C) at 23 ° C to the shear storage elastic modulus G'(60 ° C) at 60 ° C [G'(23 ° C) / G'(60 ° C)] is 1.3. The adhesive composition according to any one of claims 1 to 17, which is the above.
19. A viscous adhesive containing the cohesive adhesive composition according to any one of claims 1 to 18.
20. A sealant containing the adhesive composition according to claim 4.