TW201623535A - Hydrogenated block copolymer composition and adhesive composition - Google Patents

Abstract

The purpose of the present invention lies in providing a hydrogenated block copolymer composition which can become the adhesive composition with excellent color tone, dimension control, and cutting and excellent balance of aforementioned properties, and the adhesive composition using same. A hydrogenated block copolymer contains: the hydrogenated block copolymer containing the polymer block having the monomer unit of vinyl aromatic hydrocarbon as the main body and the conjugated diene monomer unit as the main body, and the titanium compound, wherein the content of the abovementioned titanium compound by conversion of the titanium atom is 0.000001~2 mass part relative to 100 mass part of the hydrogenated block copolymer.

Description

Hydrogenated block copolymer composition and adhesive composition

This invention relates to a hydrogenated block copolymer composition and an adhesive composition using the same.

In recent years, hot-melt adhesives have been widely used from the viewpoints of energy saving, resource saving, and environmental load reduction. As a base polymer of hot-melt adhesives, vinyl aromatic hydrocarbons are widely used. Bulk-conjugated diene single-system block copolymer (for example, SBS: styrene-butadiene-styrene-block copolymer, etc.).

For example, Patent Document 1 discloses an adhesive composition comprising a triblock copolymer and a diblock copolymer. Further, Patent Document 2 discloses an adhesive composition comprising a block copolymer obtained by coupling with a specific bifunctional coupling agent (specific dihalogen compound). Further, Patent Document 3 discloses an adhesive composition comprising a block copolymer in which a block copolymer of a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer is hydrogenated at a specific ratio.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 61-278578

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 63-248817

[Patent Document 3] Japanese Patent Laid-Open No. Hei 05-98130

However, in the above-mentioned prior art, the improvement effect of the hue, the dimensional controllability, and the cutting property is still insufficient, and further, the balance of these is not sufficient.

The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a hydrogenated block copolymer of an adhesive composition which is excellent in color tone, dimensional controllability, and cuttability, and which is excellent in balance. A composition, and an adhesive composition using the same.

The inventors of the present invention conducted intensive studies to solve the problems of the prior art described above, and as a result, found that the hydrogenated block copolymer composition of a specific structure and the viscosity of the hydrogenated block copolymer composition and the adhesion-imparting agent are respectively contained in a specific amount. The subsequent composition can solve the problems of the prior art described above, thereby completing the present invention.

That is, the present invention is as follows.

[1]

A hydrogenated block copolymer composition comprising a hydrogenated block copolymer having a polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit and a polymer block mainly composed of a conjugated diene monomer unit And titanium compounds, The content of the titanium compound is 0.000001 to 2 parts by mass based on 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom.

[2]

The hydrogenated block copolymer composition according to [1], wherein the total hydrogenation ratio of the unsaturated double bond in the above conjugated diene monomer unit is 5 mol% or more and less than 90 mol%.

[3]

The hydrogenated block copolymer composition according to [1] or [2], wherein the conjugated diene monomer unit contains a butadiene monomer unit.

[4]

The hydrogenated block copolymer composition according to any one of [1] to [3] wherein the above is ethylene The polymer block of the main aromatic hydrocarbon monomer unit has an average molecular weight of more than 7,500 and 150,000 or less.

[5]

The hydrogenated block copolymer composition according to any one of [1] to [4], wherein the content of the titanium compound is 0.000001 to 0.05 parts by mass based on 100 parts by mass of the hydrogenated block copolymer, in terms of titanium atom.

[6]

The hydrogenated block copolymer composition according to any one of [1] to [5] wherein the content of the titanium compound is more than 0.0075 parts by mass and 0.02 by mass based on 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. The following.

[7]

The hydrogenated block copolymer composition according to any one of [1] to [6] wherein the titanium compound contains at least one selected from the group consisting of titanium oxide, lithium titanate, hydrous titanium oxide, and titanium hydroxide. .

[8]

The hydrogenated block copolymer composition according to any one of [1] to [7] wherein 80 vol% or more of the titanium compound is a particle having a particle diameter of 0.1 to 100 μm.

[9]

The hydrogenated block copolymer composition according to any one of [1] to [8] wherein the hydrogenated block copolymer contains a hydrogenated block copolymer (A) and a hydrogenated block copolymer (B), The hydrogenated block copolymer (A) has the above polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit and the above polymer block mainly composed of a conjugated diene monomer unit, and the above hydrogenated block copolymer (B) having at least two of the above polymer blocks mainly composed of a vinyl aromatic hydrocarbon monomer unit and the above polymer block mainly composed of a conjugated diene monomer unit, the above hydrogenated block copolymer ( B) relative to the weight of the above hydrogenated block copolymer (A) The ratio of the average molecular weight (the weight average molecular weight of the above hydrogenated block copolymer (B)) / (the weight average molecular weight of the above hydrogenated block copolymer (A)) is from 1.3 to 10, and the above hydrogenated block copolymer (A) The content of the hydrogenated block copolymer (B) is 20% by mass or more and 90% by mass or less based on 100% by mass of the total of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). 100% by mass of the total of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) is 10% by mass or more and 80% by mass or less.

[10]

An adhesive composition comprising 100 parts by mass of the hydrogenated block copolymer composition according to any one of [1] to [9] and 20 to 700 parts by mass of the adhesion-imparting agent.

[11]

The adhesive composition according to [10], which contains an aromatic vinyl-based elastomer.

[12]

The adhesive composition according to [10] or [11], which contains a conjugated diene-based synthetic rubber.

[13]

The adhesive composition according to any one of [10] to [12] which contains natural rubber.

According to the present invention, it is possible to provide a hydrogenated block copolymer composition of an adhesive composition which is excellent in color tone, dimensional control property, and cuttability, and which is excellent in balance, and an adhesive composition using the same.

Hereinafter, the form for carrying out the invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiments, and can be carried out within the scope of the gist of the invention. Implemented with various changes.

In the following, the structural unit constituting the polymer is referred to as "~monomer unit", and when it is referred to as a material of the polymer, "unit" is omitted, and only "~ monomer" is referred to.

[Hydrogenated block copolymer composition]

The hydrogenated block copolymer composition of the present embodiment comprises a hydrogenated block copolymer comprising a polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit and a polymer block mainly composed of a conjugated diene monomer unit. In the titanium compound, the content of the titanium compound is 0.000001 to 2 parts by mass based on 100 parts by mass of the hydrogenated block copolymer.

[Hydrogenated block copolymer]

The hydrogenated block copolymer of the present embodiment contains at least one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a conjugated diene monomer unit ( D).

The weight average molecular weight of the hydrogenated block copolymer is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more. Further, the weight average molecular weight of the hydrogenated block copolymer is preferably 1,000,000 or less, more preferably 400,000 or less, still more preferably 300,000 or less. When the weight average molecular weight of the hydrogenated block copolymer is 2,000 or more, the holding power tends to be further improved. In addition, when the weight average molecular weight of the hydrogenated block copolymer is 1,000,000 or less, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition having excellent low melt viscosity characteristics and productivity. Further, the weight average molecular weight of the hydrogenated block copolymer can be determined by the method described in the examples.

In the present specification, the term "the vinyl aromatic hydrocarbon monomer unit is mainly used" means that the content of the vinyl aromatic hydrocarbon monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass. More preferably, it is 95 mass% or more. By setting the content of the vinyl aromatic hydrocarbon monomer unit in the polymer block to 60% by mass or more, a hydrogenated block copolymer composition and an adhesive composition excellent in holding power can be obtained.

In addition, in the present specification, "the conjugated diene monomer unit is the main component" means The content of the conjugated diene monomer unit in the compound block is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

The structure of the hydrogenated block copolymer is not particularly limited, and examples thereof include the following formulas (i) to (vi).

(Ar-D) _n ‧‧‧(i)

D-(Ar-D) _n ‧‧‧(ii)

Ar-(D-Ar) _n ‧‧‧(iii)

Ar-(D-Ar) _n -X‧‧‧(iv)

[(Ar-D) _k ] _m -X‧‧‧(v)

[(Ar-D) _k -Ar] _m -X‧‧‧(vi)

In the above formulas (i) to (vi), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit, and D represents a polymer mainly composed of a conjugated diene monomer unit. Block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organic lithium, and m, n and k represent an integer of 1 or more, preferably an integer of 1 to 6, respectively. . When a plurality of polymer blocks (Ar) and/or polymer blocks (D) are present, the weight average molecular weight and composition of each polymer block (Ar) and/or each polymer block (D) The structure may be the same or different. When there are a plurality of polymer blocks (Ar), it is preferable that a plurality of polymer blocks are present in terms of retention force, heat resistance, and productivity. The difference in weight average molecular weight is small. Further, it is preferred that the content of the vinyl aromatic hydrocarbon monomer unit contained in each polymer block (Ar) is divided by the number of the polymer block (Ar) and the vinyl aromatic hydrocarbon monomer unit. The difference between the value obtained by dividing the content of the hydrogenated block copolymer by the number of polymer blocks (Ar) is small.

The difference in weight average molecular weight of the plurality of polymer blocks (Ar) present is not particularly limited, and the weight average molecular weight of the other polymer block (Ar) relative to the polymer block (Ar) having the largest weight average molecular weight Preferably, the difference between the weight average molecular weight of the polymer block (Ar) having the largest weight average molecular weight is 35% or less, more preferably 25% or less. It is preferably 15% or less, and more preferably 5% or less. Further, it is not particularly limited, but is preferably 0% or more.

Further, the weight average molecular weight of the polymer block (Ar) can be determined by the measurement method described in the examples.

The content of the vinyl aromatic hydrocarbon monomer unit contained in each polymer block (Ar) divided by the number of polymer blocks (Ar) and the hydrogenated block copolymerization of the vinyl aromatic hydrocarbon monomer unit The difference between the content of the polymer block (Ar) and the amount of the polymer block (Ar) is not particularly limited, and it is preferably the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer. The value obtained by dividing the number of the polymer blocks (Ar) is 7% or less, more preferably 5% or less, further preferably 3% or less, and still more preferably 1% or less. Further, it is not particularly limited, but is preferably 0% or more.

Further, the content of the monomer unit of the vinyl aromatic compound contained in each polymer block (Ar) can be obtained by polymerization of the polymer block (Ar) and the polymer block (D). At the end of the extraction, a small amount was extracted, and the content of the vinyl aromatic hydrocarbon monomer unit was measured by the method described in the examples, and the calculation was carried out in consideration of the structure of the finally obtained hydrogenated block copolymer.

The content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer of the present embodiment is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more. Further, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less. When the content of the vinyl aromatic hydrocarbon monomer unit is in the above range, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition which have excellent adhesion properties and are excellent in balance. In particular, when the content of the vinyl aromatic hydrocarbon monomer unit is 5% by mass or more, there is a tendency to obtain a hydrogenated block copolymer having excellent holding power. In addition, when the content of the vinyl aromatic hydrocarbon monomer unit is 95% by mass or less, a hydrogenated block copolymer and an adhesive composition having excellent viscosity and productivity tend to be obtained. to When it is used for a tape or the like, it is preferably 10% by mass or more, more preferably 12% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less. When it is used for applications such as adhesive labeling, it is preferably 10% by mass or more, preferably 12% by mass or more, more preferably 18% by mass or more, preferably 35% by mass or less, and more preferably 30% by mass. the following. When it is used for applications such as sanitary materials, it is preferably 12% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, preferably 70% by mass or less, and more preferably 68% by mass. %the following. When the content of the vinyl aromatic hydrocarbon monomer unit is in the above range, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition which have excellent adhesion properties and are excellent in balance. Further, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer can be measured by the method described in the following examples.

Further, the ethylene bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer of the present embodiment is preferably 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. Further, the ethylene bond amount of the conjugated diene monomer unit before hydrogenation is preferably 15 mol% or more, more preferably 18 mol% or more, still more preferably 20 mol% or more. More specifically, the amount of the ethylene bond of the conjugated diene monomer unit before hydrogenation of the hydrogenated block copolymer is preferably 15 mol% or more and 95 mol% or less, more preferably 18 mol% or more and 90 mol% or less. It is preferably 20 mol% or more and 85 mol% or less. When the ethylene bond amount of the conjugated diene monomer unit is within the above range, the properties excellent in productivity and adhesion characteristics tend to be obtained.

Here, the amount of the ethylene bond means the total amount of the conjugated diene monomer unit incorporated in the bonding manner of the 1,2-bond and the 3,4-bond before hydrogenation relative to 1,2. The ratio of the total amount of the conjugated diene monomer units incorporated in the bonding manner of the bond, the 3,4-bond and the 1,4-bond. Further, after hydrogenation, the unhydrogenated 1,2-bond, the hydrogenated 1,2-bond, the unhydrogenated 3,4-bond and the hydrogenated 3,4-bond bond are incorporated. The total amount of the conjugated diene monomer unit is relative to the unhydrogenated 1,2-bond, the hydrogenated 1,2-bond, the unhydrogenated 3,4-bond, the hydrogenated 3,4-bond, a conjugated diene incorporated in an unhydrogenated 1,4-bond and a hydrogenated 1,4-bond bond The ratio of the total mol amount of the monomer unit is equal to the ethylene bond amount of the conjugated diene monomer unit before hydrogenation. Therefore, the ethylene bond amount of the conjugated diene monomer unit before hydrogenation can be measured by nuclear magnetic resonance spectroscopy (NMR) using the hydrogenated block copolymer, specifically, as described in the following examples. Determined by the method.

Further, the content of the vinyl aromatic hydrocarbon monomer unit and the weight average molecular weight are substantially the same values before and after the hydrogenation, and therefore the value after hydrogenation is employed.

The conjugated diene monomer unit before hydrogenation can be controlled in the polymerization step by using a polar compound or a randomizer as described below.

In the hydrogenation step, the conjugated bond of the vinyl aromatic hydrocarbon monomer unit can be hydrogenated, but the hydrogenation ratio of the conjugated bond of all the vinyl aromatic hydrocarbon monomer units is higher from the viewpoint of retention or adhesion. It is preferably 30 mol% or less, more preferably 10 mol% or less, still more preferably 3 mol% or less.

In addition, the total hydrogenation ratio of the unsaturated double bond in the conjugated diene monomer unit in the hydrogenated block copolymer of the present embodiment is preferably 5 mol% or more from the viewpoint of holding strength and viscosity. More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more. Further, the total hydrogenation ratio of the unsaturated double bond in the conjugated diene monomer unit in the hydrogenated block copolymer is preferably less than 90 mol%, more preferably 88 mol%, from the viewpoint of low melt viscosity. Hereinafter, it is more preferably 87 mol% or less. When the hydrogenation ratio is 5 mol% or more, a hydrogenated block copolymer having excellent holding power and viscosity tends to be obtained. Moreover, by making the hydrogenation ratio less than 90 mol%, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition having excellent viscosity and low melt viscosity characteristics. Further, the hydrogenation ratio of the conjugated diene monomer unit in the hydrogenated block copolymer can be measured by the method described in the examples.

Further, in the polymer block (Ar) of the present embodiment, the content of the vinyl aromatic hydrocarbon monomer unit which is 25 or more is preferably 90% by mass or more, more preferably 93% by mass or more, and further It is preferably 95% by mass or more, and more preferably 98% by mass or more. Moreover, it is preferably 100% by mass or less, but is not particularly limited. In the polymer block (Ar), by making When the content of the vinyl aromatic hydrocarbon monomer unit of 25 or more is in the above range, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition which have excellent adhesion properties and excellent balance. . In particular, when the content is 90% by mass or more, a hydrogenated block copolymer having excellent retention and heat resistance tends to be obtained. In addition, when the content is 100% by mass or less, a hydrogenated block copolymer and an adhesive composition having excellent productivity tend to be obtained. Further, the content of the vinyl aromatic hydrocarbon monomer unit which is 25 or more is a polymer block component containing a vinyl aromatic hydrocarbon monomer unit which is obtained by the measurement method described in the examples. The weight (wherein the vinyl aromatic polymer component having an average degree of polymerization of 24 or less was removed) was determined.

Further, the average molecular weight of the polymer block (Ar) mainly composed of the vinyl aromatic hydrocarbon monomer unit of the present embodiment is preferably more than 7,500, more preferably 8,000 or more, still more preferably 10,000 or more, and still more preferably It is 11,500 or more. Further, the average molecular weight of the polymer block (Ar) is preferably 150,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, still more preferably 20,000 or less. By making the average molecular weight of the polymer block (Ar) more than 7,500, there is a tendency to obtain a hydrogenated block copolymer having excellent retention. Moreover, by making the average molecular weight of the polymer block (Ar) 150,000 or less, there is a tendency to obtain a hydrogenated block copolymer and an adhesive composition having excellent viscosity. Here, the "average molecular weight of the polymer block (Ar)" refers to the molecular weight of the block when the polymer block (Ar) contained in the hydrogenated block copolymer is one. When the number of the block (Ar) is two or more, it means the average molecular weight of the blocks. The average molecular weight of the polymer block (Ar) can be controlled within the above range by adjusting the conditions of the following production methods. Further, the average molecular weight of the polymer block (Ar) can be measured by the method described in the examples.

The hydrogenated block copolymer of the present embodiment may contain the following hydrogenated block copolymer (A) from the viewpoint of improving the balance between the adhesive properties and the low melt viscosity characteristics (hereinafter also referred to as "component (A) ") and hydrogenated block copolymer (B) (hereinafter also referred to as "ingredient (B)") A hydrogenated block copolymer having two different structures. Here, component (A) is a hydrogenated block polymer containing at least one polymer block (Ar) and at least one polymer block (D), and component (B) contains at least two polymer blocks (Ar) a hydrogenated block polymer with at least one polymer block (D).

The content of the component (A) is preferably 20% by mass or more and 90% by mass or less, more preferably 25% by mass or more and 85% by mass or less based on 100% by mass of the total of the component (A) and the component (B). Further, it is preferably 30% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 75% by mass or less.

The content of the component (B) is preferably 100% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less based on 100% by mass of the total of the component (A) and the component (B). Further, it is preferably 20% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 60% by mass or less.

By setting the content of the component (A) and the component (B) within the above range, a hydrogenated block copolymer composition and a binder combination which are excellent in low melt viscosity characteristics and adhesion characteristics and which are excellent in balance are also obtained. The tendency of things. Further, the content of the component (A) and the component (B) can be controlled within the above range by adjusting the conditions of the following production methods. Further, the contents of the component (A) and the component (B) can be measured by the methods described in the following examples. Further, the values of the contents of the component (A) and the component (B) are substantially the same values before and after the hydrogenation, and the values after hydrogenation are used.

When the component (A) and the component (B) are contained, the ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) [(weight average molecular weight of the component (B)) / (component ( The weight average molecular weight) of A) is 1.3 or more and 10 or less, preferably 1.5 or more and 8.0 or less, more preferably 1.8 or more and 5.0 or less. By setting the ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) within the above range, it is possible to obtain a low melt viscosity characteristic and an excellent adhesion property, and also have excellent balance. The tendency of the segmented copolymer composition and the adhesive composition.

Content of component (A) and component (B), weight average molecular weight, and weight average molecular weight The ratio can be controlled within the above range by adjusting the conditions of the following manufacturing methods. Further, the ratio of the content of the component (A) and the component (B), the weight average molecular weight, and the weight average molecular weight can be measured by the methods described in the following examples.

As the hydrogenated block copolymer, when the component (A) or the component (B) is contained, the content of the vinyl aromatic hydrocarbon monomer unit does not mean the value of each component, but is a hydrogenated block copolymerization. The total content, that is, the average of the contents of the ingredients.

When the hydrogenated block copolymer contains the component (A) or the component (B), the ethylene bond amount of the conjugated diene monomer unit before hydrogenation does not mean the value of each component, but is used as a hydrogenation. The ethylene bond amount of the block copolymer as a whole, that is, the average value of the ethylene bond amount of each component.

Further, the total hydrogenation ratio of the unsaturated double bonds in the conjugated diene monomer unit in the hydrogenated block copolymer also does not refer to the value of each component, but is the ethylene bond amount of the hydrogenated block copolymer as a whole, that is, The average of the amount of ethylene bonds of each component.

Hereinafter, each component will be described in more detail.

(ingredient (A))

The component (A) preferably contains at least one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block (D) mainly composed of a conjugated diene monomer unit. .

The weight average molecular weight of the hydrogenated block copolymer of the component (A) is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more. Further, the weight average molecular weight of the hydrogenated block copolymer of the component (A) is preferably 500,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less. When the weight average molecular weight of the component (A) is 2,000 or more, the holding power and the productivity are excellent, and by setting the weight average molecular weight of the component (A) to 500,000 or less, excellent low melt viscosity characteristics can be obtained. The hydrogenated block copolymer composition and the adhesive composition. Further, the weight average molecular weight of the component (A) can be determined by the method described in the examples.

The structure of the component (A) is not particularly limited, and examples thereof include the following formulas (i) to (vi).

(Ar-D) _n ‧‧‧(i)

D-(Ar-D) _n ‧‧‧(ii)

Ar-(D-Ar) _n ‧‧‧(iii)

Ar-(D-Ar) _n -X‧‧‧(iv)

[(Ar-D) _k ] _m -X‧‧‧(v)

[(Ar-D) _k -Ar] _m -X‧‧‧(vi)

(In the above formulae (i) to (vi), Ar represents a polymer block (Ar), D represents a polymer block (D), and X represents a polymerization agent residue or a polyfunctional organic lithium polymerization. The residues of the initiator, m, n and k are integers of 1 or more, preferably each of an integer of 1 to 6. When there are plural cases, the types of the vinyl aromatic hydrocarbon monomers of Ar may be the same. The type or molecular weight of the conjugated diene monomer of D may be the same or different when there are a plurality of cases, and the above aspect may be preferably used in the case where a plurality of Ar are present)

In the above formulas (i) to (vi), a hydrogenated block copolymer containing a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit is preferred, and more preferably Ar-D, A hydrogenated block copolymer represented by D-Ar-D. By having such a structure of the component (A), there is a tendency to obtain a hydrogenated block copolymer composition and an adhesive composition which have excellent low melt viscosity characteristics and adhesive strength and are excellent in balance.

(ingredient (B))

The component (B) preferably contains at least two polymer blocks (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a conjugated diene monomer unit (D). ).

The weight average molecular weight of the hydrogenated block copolymer of the component (B) is preferably 4,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more. Further, the weight average molecular weight of the hydrogenated block copolymer of the component (B) is preferably 1,000,000 or less, more preferably 400,000. Further, it is preferably 300,000 or less. When the weight average molecular weight of the component (B) is 4,000 or more, the retention or productivity tends to be further improved. In addition, when the weight average molecular weight of the component (B) is 1,000,000 or less, the hydrogenated block copolymer composition and the adhesive composition having excellent low melt viscosity characteristics tend to be obtained. Further, the weight average molecular weight of the component (B) can be determined by the method described in the examples.

In addition, the structure of the component (B) is not particularly limited, and examples thereof include the following formulas (vii) to (xii).

(Ar-D) _e ‧‧‧(vii)

D-(Ar-D) _e ‧‧‧(viii)

Ar-(D-Ar) _g ‧‧‧(ix)

[Ar-(D-Ar) _g ] _f -X‧‧‧(x)

[D-(Ar-D) _g ] _f -X‧‧‧(xi)

[(Ar-D) _g ] _f -X‧‧‧(xii)

[(Ar-D) _g -Ar] _f -X‧‧‧(xiii)

(In the above formulas (vii) to (xiii), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit, and D represents a polymerization mainly composed of a conjugated diene monomer unit. The block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organic lithium, and e and f represent an integer of 2 or more, and g represents an integer of 1 or more, preferably The number of the vinyl aromatic hydrocarbon monomers of Ar may be the same or different when there are a plurality of positive integers of 6 or less, and the type of the conjugated diene monomer of D in the case of plural cases or The molecular weights may be the same or different, and in the case where a plurality of Ar are present, the above aspect may be preferably used)

In the above formulas (vii) to (xiii), hydrogenation represented by the formulas (vii), (ix), (xi), (xii) (e = 2, g = 1, f = 2 to 4) is preferred. Block copolymer. By having such a structure of the component (B), there is a tendency to further improve the balance of the adhesion properties and the productivity.

[Method for Producing Hydrogenated Block Copolymer]

The hydrogenated block copolymer can be produced by sequentially performing the following steps: using an organolithium compound as a polymerization initiator in a hydrocarbon solvent, at least a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer are polymerized to obtain a polymer. a polymerization step; a hydrogenation step of hydrogenating a double bond in a conjugated diene monomer unit of the obtained polymer; and a solvent removal step of desolvating a solvent containing a solution of the hydrogenated block copolymer. The weight average molecular weight of the hydrogenated block copolymer can be adjusted, for example, by controlling the kind or addition amount of the coupling agent described below. Further, the weight average molecular weight may be adjusted by controlling the addition amount and the number of additions of the polymerization initiator described below in a plurality of additions.

When the hydrogenated block copolymer contains two hydrogenated block copolymers having two different structures of the component (A) and the component (B), the component (A) and the component (B) may be separately produced, and then Mix again or at the same time. In the case where the component (A) and the component (B) are simultaneously produced, the ratio of the weight average molecular weight and the weight average molecular weight of the component (A) to the component (B) and the content can be controlled, for example, by controlling the type or addition of the coupling agent described below. Adjusted by quantity. Further, the ratio of the weight average molecular weight and the weight average molecular weight of the component (A) to the component (B) and the content of the component (B) can be adjusted by controlling the addition amount and the number of additions of the polymerization initiator described below. Further, the temporary deactivation step can be carried out by controlling the addition amount of the deactivator described below, and the polymerization reaction can be continued, and the ratio and content of the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) can be adjusted.

(aggregation step)

The polymerization step is a step of obtaining a polymer by polymerizing at least a monomer containing a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer as a polymerization initiator in a hydrocarbon solvent.

The polymerization temperature is usually from 10 to 150 ° C, preferably from 30 to 130 ° C, more preferably from 40 to 100 ° C. The polymerization pressure is not particularly limited as long as it is carried out within a sufficient pressure range required to maintain the monomer and the solvent in the liquid phase within the above polymerization temperature range. The time required varies depending on the conditions, usually within 48 hours, preferably 0.5 to 10 hours. Time.

<hydrocarbon solvent>

As described above, a hydrocarbon solvent is used in the polymerization step. The hydrocarbon solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane, methylcyclopentane, and cyclohexane. An alicyclic hydrocarbon such as methylcyclohexane or ethylcyclohexane; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene or xylene. The hydrocarbon solvent may be used singly or in combination of two or more.

<Polymerization initiator>

In the polymerization step, at least an organolithium compound is used as a polymerization initiator. The organolithium compound is not particularly limited, and examples thereof include an organic monolithium compound in which one or more lithium atoms are bonded to a molecule, an organic dilithium compound, and an organic polylithium compound. More specifically, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl group Dilithium, isopentenyldilithium, and the like. The polymerization initiator may be used alone or in combination of two or more.

The polymerization initiator can be added to the reaction solution in plural times. Thereby, a composition containing a plurality of block copolymers having a weight average molecular weight or a structure different can be temporarily obtained.

<Monomer used in polymerization>

The conjugated diene single system constituting the polymer block (D) has a diene of one pair of conjugated double bonds. The conjugated diene monomer is not particularly limited, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-dimethyl Base-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like. Among them, preferred are 1,3-butadiene and isoprene. Further, from the viewpoint of improving the retaining power of the adhesive composition, 1,3-butadiene is more preferable. The conjugated diene monomer may be used alone or in combination of two or more.

The vinyl aromatic hydrocarbon monomer constituting the polymer block (Ar) is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, and 1,1. -stilbene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-pair Aminoethyl styrene and the like. Among them, styrene is preferred in terms of economy. The vinyl aromatic hydrocarbon monomers may be used alone or in combination of two or more.

The block copolymer may contain a monomer unit other than the vinyl aromatic hydrocarbon monomer unit and the conjugated diene monomer unit, and in addition to the vinyl aromatic hydrocarbon monomer and the conjugated diene monomer, in the polymerization step, Other monomers that can be copolymerized with the monomer can be used.

<Polar compound and randomizer>

In the polymerization step, for the adjustment of the polymerization rate, the control of the microstructure (the ratio of the cis, the reverse, the vinyl group) of the polymerized conjugated diene monomer unit, the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer For the purpose of adjusting the reaction ratio, a specific polar compound or a randomizer can be used.

The polar compound or the randomizer is not particularly limited, and examples thereof include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; and triethylamine and tetramethylethylenediamine. Amines; thioethers, phosphines, phosphoniumamines, alkylbenzenesulfonates, potassium or sodium alkoxides, and the like.

<coupling agent>

In the polymerization step, in the solution containing the vinyl aromatic-conjugated diene block copolymer having an active terminal, the functional group may be added to the above formula in an amount of less than 1 mol equivalent relative to the active terminal. (iv) The coupling agent represented by X in ~(vi), (x)~(xiii).

The coupling agent to be added is not particularly limited, and any of a difunctional or higher coupling agent can be used. The bifunctional coupling agent is not particularly limited, and examples thereof include difunctional halogenated decane such as dichlorodecane, monomethyldichlorodecane or dimethyldichlorodecane; diphenyldimethoxydecane and Bifunctional alkoxydecane such as phenyldiethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane; dichloroethane, dibromoethane, dichloromethane, dibromomethane Difunctional halogenated alkane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyltin dichloride, dibutyl chlorine Bifunctional tin halide such as tin; dibromobenzene, benzoic acid, CO, 2-chlorobenzene, and the like.

The trifunctional coupling agent is not particularly limited, and examples thereof include a trifunctional halogenated alkane such as trichloroethane or trichloropropane; a trifunctional halogenated decane such as methyltrichlorodecane or ethyltrichlorodecane; a trifunctional alkoxydecane such as a methoxymethoxydecane, a phenyltrimethoxydecane or a phenyltriethoxydecane; and the like.

The tetrafunctional coupling agent is not particularly limited, and examples thereof include tetrafunctional halogenated alkane such as carbon tetrachloride, carbon tetrabromide and tetrachloroethane; and tetrafunctional halogenated decane such as tetrachlorodecane or tetrabromodecane. a tetrafunctional alkoxydecane such as tetramethoxynonane or tetraethoxysilane; a tetrafunctional tin halide such as tetrachlorotin or tetrabromotin; and the like.

The pentafunctional or higher coupling agent is not particularly limited, and examples thereof include 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, and octabromodiphenyl ether. , decabromodiphenyl ether and the like. Further, a epoxidized soybean oil, a 2- to 6-functional epoxy group-containing compound, a carboxylic acid ester, or a divinylbenzene-based polyethylene compound can also be used. The coupling agent may be used alone or in combination of two or more.

Among the above, a non-halogen coupling agent is preferred from the viewpoint of color tone and low adverse effect on equipment. Further, from the viewpoint of productivity or low adverse effects on equipment, an epoxy group-containing compound or alkoxydecane is preferred.

As described above, in the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal, the coupling agent is added in an amount of less than 1 mol equivalent relative to the active terminal. In one part of the block copolymer of the aromatic vinyl-conjugated diene block copolymer having an active terminal, the living terminals are bonded to each other via a residue of a coupling agent. Further, the remaining portion of the vinyl aromatic-conjugated diene block copolymer having an active terminal remains in the solution in an unreacted state. In the reaction using the coupling agent, the coupling ratio can be controlled by adjusting the type or amount of the coupling agent.

The polymerization method to be carried out in the polymerization step in the method for producing a polymer of the present embodiment is not particularly limited, and a known method can be applied, and for example, a Japanese patent can be cited. Japanese Patent Publication No. Sho 36-19286, Japanese Patent Publication No. Sho 43-17979, Japanese Patent Publication No. Sho 46-32415, Japanese Patent Publication No. Sho 49-36957, Japanese Patent Publication No. Sho 48-2423, Japanese Patent The method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

<inactivation agent>

An inactivating agent may also be added during the polymerization step. The deactivator is not particularly limited, and water or an alcohol or the like is known. Among them, from the viewpoint of the efficiency of deactivation, an alcohol is preferred. The deactivating agent can be added at any point in the polymerization step. If the amount of the deactivator added is less than 100 mol% of the active end, the conjugated diene monomer and/or the vinyl aromatic hydrocarbon monomer may be further added after the addition of the deactivator. Thus, the polymerization reaction of the unactivated active terminal with the conjugated diene monomer and/or the vinyl aromatic hydrocarbon monomer is continued, and a polymer solution containing a polymer having a different molecular weight can be obtained.

Further, in the case of having two kinds of hydrogenated block copolymers having different structures of the component (A) and the component (B), the contents of the component (A) and the component (B) in the deactivation step can be adjusted by It is controlled with respect to the addition amount of the deactivating agent of the addition amount of the polymerization initiator. The more the amount of the molar amount of the deactivator added, the more the content of the component (A) becomes, and the smaller the amount of the molar amount of the deactivator is, the smaller the content of the component (B) tends to be.

Further, the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) can be controlled by adding a conjugated diene monomer and/or a vinyl aromatic hydrocarbon monomer after the addition of the deactivating agent to continue the polymerization reaction. Ratio. Specifically, the more the amount of the conjugated diene monomer and/or the vinyl aromatic hydrocarbon monomer added after the addition of the deactivator, the larger the weight average molecular weight of the component (B) becomes, and the weight The ratio of the average molecular weight also tends to be large.

(hydrogenation step)

The hydrogenation step is a step of subjecting the double bond in at least the conjugated diene monomer of the polymer obtained in the polymerization step to a hydride by a hydrogenation reaction. Specifically, it can be used in an inert solvent Hydrogenation is carried out in the presence of a hydrogenation catalyst to obtain a hydrogenated block copolymer solution. At this time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, the reaction time, the amount of hydrogen supplied, the amount of the catalyst, and the like.

The catalyst used in the hydrogenation reaction is not particularly limited. For example, it is known that (1) a metal such as Ni, Pt, Pd or Ru is supported on a carrier such as carbon, cerium oxide, alumina or diatomaceous earth. a supported type heterogeneous catalyst, and (2) a so-called Ziegler type catalyst using an organic salt such as Ni, Co, Fe, Cr or the like, or a reducing agent such as an ethyl acetonide salt or an organic Al, or Ru, Rh. A so-called organic complex catalyst such as an organometallic compound, or a homogeneous catalyst such as organic Li, organic Al, or organic Mg as a reducing agent is used for the titanocene compound. Among them, from the viewpoints of economy, coloring property of the polymer, or adhesion, it is preferred to use a uniform catalyst such as organic Li, organic Al, or organic Mg as a reducing agent in the titanocene compound.

The hydrogenation reaction temperature is preferably from 0 to 200 ° C, more preferably from 30 to 150 ° C. Further, the pressure of hydrogen used in the hydrogenation reaction is preferably from 0.1 to 15 MPa, more preferably from 0.2 to 10 MPa, still more preferably from 0.3 to 5 MPa. Further, the hydrogenation reaction time is preferably from 3 minutes to 10 hours, more preferably from 10 minutes to 5 hours. Further, the hydrogenation reaction can be either a batch process, a continuous process, or a combination of the two.

The hydrogenation method is not particularly limited, and examples thereof include a Japanese Patent Publication No. Sho 42-8704, a Japanese Patent Publication No. Sho 43-6636, a Japanese Patent Publication No. Sho. No. 63-4841, and a Japanese Patent Publication No. 63-5401. The method described in the bulletin.

The hydrogenation reaction is not particularly limited, and from the viewpoint of high hydrogenation activity, it is preferably carried out after the step of deactivating the active terminal of the following polymer.

(desolvation step)

The solvent removal step is a step of desolvating a hydrocarbon solvent containing a solution of a polymer. The solvent removal method is not particularly limited, and examples thereof include a solvent removal method by a steam stripping method or a direct solvent removal method.

The amount of residual solvent in the polymer obtained by the above method for producing a polymer The content is preferably 2% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.05% by mass or less, and still more preferably 0.01% by mass or less.

Further, from the viewpoint of suppressing heat aging resistance or gelation of the block copolymer of the present embodiment, it is preferred to add an antioxidant. The antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant of a radical scavenger, a phosphorus-based antioxidant of a peroxide decomposer, and a sulfur-based antioxidant. Further, an antioxidant having both properties can also be used. These may be used singly or in combination of two or more. Among them, from the viewpoint of suppressing heat aging resistance or gelation of the polymer, it is preferred to add at least a phenol antioxidant.

Further, in terms of color prevention of the polymer or high mechanical strength, a step of removing the ash from the metal in the polymer or adjusting the pH of the polymer may be performed, for example, an acid addition or The addition of carbon dioxide.

The hydrogenated block copolymer of the present embodiment which can be produced by the above method may comprise: a functional group and a block having a polar group containing an atom selected from the group consisting of nitrogen, oxygen, helium, phosphorus, sulfur, and tin. A so-called modified polymer in which a copolymer is bonded, or a modified block copolymer in which a block copolymer component is modified with a modifier such as maleic anhydride. Such a modified copolymer can be obtained by subjecting a hydrogenated block copolymer obtained by the above method to a known modification reaction.

The method of imparting the functional groups is not particularly limited, and examples thereof include a method of adding a functional group to a polymer by using a compound having a functional group in a starter, a monomer, a coupling agent or a terminator.

The initiator containing a functional group is not particularly limited, and for example, an initiator containing an N group is preferred, and examples thereof include lithium dioctylamine, lithium di-2-ethylhexylamine, and ethylbenzylamine. Lithium, (3-(dibutylamino)-propyl)lithium, piperidinyllithium, and the like.

Further, the monomer having a functional group is not particularly limited, and examples thereof include a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, a decyl alcohol group, and an alkyl group in the monomer used in the polymerization. a compound of an oxoalkyl group. Among them, a monomer having an N group is preferred, and examples thereof include N,N-dimethylvinylbenzylamine, N,N-diethylvinylbenzylamine, and N,N-dipropylvinylbenzylamine. N,N-dibutylvinylbenzylamine, N,N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-double ( Trimethyldecyl)aminoethylstyrene, 1-(4-N,N-dimethylaminophenyl)-1-styrene, N,N-dimethyl-2-(4-vinyl Benzyloxy)ethylamine, 4-(2-pyrrolidinylethyl)styrene, 4-(2-piperidinylethyl)styrene, 4-(2-hexamethyleneiminoethyl)benzene Ethylene, 4-(2- Lolinylethyl)styrene, 4-(2-thiazide Benzyl)styrene, 4-(2-N-methylpiperidine Ethyl ethyl) styrene, 1-((4-vinylphenoxy)methyl)pyrrolidine, 1-(4-vinylbenzyloxymethyl)pyrrolidine, and the like.

Further, the coupling agent and the terminator containing a functional group are not particularly limited, and examples thereof include a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, a decyl alcohol group, and an alkoxy group in the above coupling agent. a compound of a decyl group or the like. Among them, a coupling agent containing an N group or an O group is preferred, and examples thereof include tetraglycidyl metaxylylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, and tetraglycidyl pair. Phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidoxyethyltrimethoxydecane, γ-glycidoxypropyltrimethyl Oxydecane, γ-glycidoxypropyltriphenoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropyldiethylethoxydecane, 1,3-Dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylpropylurea, N-methylpyrrolidone, and the like.

[titanium compound]

The hydrogenated block copolymer composition of the present embodiment contains a titanium compound. The content of the titanium compound is 0.000001 to 2 parts by mass based on 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. The term "calcium atom conversion" as used herein means the amount of titanium atoms in a titanium compound containing a compound such as titanium oxide or lithium titanate. Specifically, it can be measured by the method described in the examples.

The type of the titanium compound is not particularly limited, and examples thereof include rutile Type, anatase, brookite-type crystalline titanium oxide; amorphous titanium oxide, orthotitanic acid or metatitanic acid; such as titanium hydroxide, lithium titanate, barium titanate, titanium A composite oxide of titanium and a dissimilar metal of acid. Among them, the titanium compound preferably contains at least one selected from the group consisting of titanium oxide, titanium hydroxide, titanium hydroxide, and lithium titanate. By using such a titanium compound, there is a tendency that the color tone is further optimized. These may be used alone or in combination of two or more.

Further, the titanium compound may contain a reactant of a titanium compound used as a hydrogenation catalyst of a conjugated diene polymer. By using such a titanium compound, there is a tendency to further optimize economy and productivity. Specifically, when the block copolymer is subjected to a hydrogenation reaction using a titanium compound to obtain a hydrogenated block copolymer, the hydrogenated block copolymer may contain a titanium compound. Therefore, for example, the titanium compound can be prepared as a titanium compound having a particle diameter of 0.1 to 100 μm and the content of the titanium compound can be controlled to 0.000001 to 2 parts by mass. Specifically, a method in which a titanium compound as a catalyst is brought into contact with, for example, water to form a titanium oxide, and the particles of the obtained titanium oxide are grown to a specific particle diameter. Further, when the titanium compound particles are grown by contact with water, depending on the content of the titanium compound or the amount of water, the particles tend to grow as the contact time or frequency increases. Further, the content of the titanium compound can be controlled by a method such as filtration.

The content of the titanium compound having a particle diameter of 0.1 μm or more and 100 μm or less is preferably 80 vol% or more, more preferably 85 vol% or more, and still more preferably 90 vol% or more, based on 100 vol% of the total amount of the titanium compound. The upper limit of the content of the titanium compound having a particle diameter of 0.1 μm or more and 100 μm or less is not particularly limited, but is preferably 100 vol% or less. By having such a particle size distribution, there is a tendency to obtain a hydrogenated block copolymer composition and an adhesive composition which are excellent in adhesion characteristics, dimensional control properties, and cutting properties. In the case where the hydrogenated block copolymer composition contains a metal compound particle other than the titanium compound, for example, when the metal compound contains a titanium compound or a lithium compound, the above-mentioned "particle diameter is 0.1 μm or more and 100 μm or less. The content of the titanium compound is alternatively understood to mean "the particle diameter is 0.1 μm or more, The content of the metal compound below 100 μm".

In addition, the content of the titanium compound having a particle diameter of 0.1 μm or more and 50 μm or less is preferably 80 vol% or more and 100 vol% or less with respect to 100 vol% of the total amount of the titanium compound, and more preferably 0.1 μm or more and 30 μm or less. The content of the titanium compound is 80 vol% or more and 100 vol% or less based on 100 vol% of the total amount of the titanium compound. By having such a particle size distribution, there is a tendency to obtain a hydrogenated block copolymer composition and an adhesive composition which are excellent in dimensional controllability and cuttability. In the case where the hydrogenated block copolymer composition contains a metal compound particle other than the titanium compound, for example, when the metal compound contains a titanium compound or a lithium compound, the above-mentioned "particle diameter is 0.1 μm or more and 50 μm or less. The content of the titanium compound is alternatively understood to mean "the content of the metal compound having a particle diameter of 0.1 μm or more and 50 μm or less".

The content of the titanium compound is 0.000001 parts by mass, preferably 0.00001 parts by mass or more, more preferably 0.0001 parts by mass or more, and still more preferably 0.0005 parts by mass or more, based on 100 parts by mass of the hydrogenated block copolymer. More preferably, it is more than 0.0075 parts by mass. In addition, the content of the titanium compound is 2 parts by mass or less based on 100 parts by mass of the hydrogenated block copolymer, and is preferably 1 part by mass or less, and preferably 0.05 or less, from the viewpoint of holding strength and viscosity. The amount by mass or less is more preferably 0.025 parts by mass or less, further preferably 0.02 parts by mass or less. When the content of the titanium compound is 0.000001 parts by mass or more, the color tone, the dimensional control property, and the cutting property tend to be excellent, and when the content is 2 parts by mass or less, excellent productivity is obtained, which is economically advantageous. The tendency of the hydrogenated block copolymer composition and the adhesive composition. Moreover, when the content of the titanium compound exceeds 2 parts by mass, the retaining power and the viscosity of the adhesive composition tend to be impaired.

The average particle diameter of the titanium compound is preferably from 0.1 to 50 μm, more preferably from 0.1 to 30 μm, still more preferably from 0.1 to 20 μm. By such an average particle diameter, excellent color tone, dimensional controllability, cutting property, and a good balance of these adhesion characteristics can be obtained.

The content of the titanium compound can be determined by the method described in the following examples. also, The average particle diameter of the titanium compound contained in the conjugated diene polymer can be determined by analyzing the polymer solution obtained by dissolving the titanium-containing composition in an inert solvent by a laser diffraction type particle size distribution meter. More specifically, it can be obtained by the method described in the examples.

Further, when the titanium-containing composition contains other metal compound particles other than the titanium compound, for example, when the metal compound contains a titanium compound and a lithium compound, the "particle size of the titanium compound" may be replaced by the word "metal compound". Particle size." Here, the "particle diameter of the metal compound" means the particle diameter of the particle containing the titanium compound and another metal compound, or the particle diameter of the titanium compound particle and another metal compound particle.

The method for producing the hydrogenated block copolymer containing a titanium compound or the hydrogenated block copolymer composition containing a titanium compound is not particularly limited, and examples thereof include a method in which a solid is used using a Plastomill, an extruder, a roll, or the like. a method in which a conjugated diene polymer is mixed with a titanium compound, thereby being dispersed in a hydrogenated block copolymer or a hydrogenated block copolymer composition; and a polymerization in which a hydrogenated block copolymer or a hydrogenated block copolymer composition is dissolved A method of adding a titanium compound to a solution of a solution, and then removing the solvent by heating or depressurizing the solution; adding a titanium alkoxide and water to the polymer solution to hydrolyze the alkoxide, and forming a titanium compound or the like in the system . At this time, the particle diameter can be controlled by controlling the mixing method (stirring method). Further, as described above, a hydrogenated block copolymer containing a titanium compound or a hydrogenated embedded titanium compound may be prepared by forming a titanium compound having a particle diameter of 0.1 to 100 μm in a hydrogenated block copolymer or a hydrogenated block copolymer composition. Segment copolymer composition.

[Adhesive composition]

The adhesive composition of the present embodiment preferably contains 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition, 20 to 700 parts by mass of the following adhesion-imparting agent, and the following other components as necessary. . The adhesive composition of the present embodiment is an adhesive composition having excellent holding power, viscosity, low melt viscosity characteristics, color tone, dimensional controllability, and cutting property, and the balance of these is excellent.

Furthermore, the adhesive composition of the present embodiment may contain the component (A) and the component (B). External polymer (for example, polyolefin; polyolefin copolymer; styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene system Segment copolymer, hydrogenated styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene block An aromatic vinyl-based elastomer such as a copolymer; other rubbers, etc.). In this case, the following adhesion-imparting agent is 20 to 500 parts by mass with respect to the total content of the polymer (100% by mass) of the component (A) and the component (B) of the present embodiment, and the following softener is : 0 to 300 parts by mass.

Further, it is preferred to select the weight average molecular weight of the components (A) and (B) in the hydrogenated block copolymer composition according to the use, and to adjust the blending amount of each component such as the tackifier and the softener.

(adhesive agent)

The adhesion-imparting agent can be variously selected depending on the use and required properties of the obtained adhesive composition. The adhesive agent is not particularly limited, and examples thereof include natural rosin, modified rosin, glycerin of natural rosin, glycerin of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin, a rosin-based compound such as a hydrogenated rosin pentaerythritol ester; a copolymer of a natural terpene, a terpolymer of a natural terpene, an aromatic modified terpene resin, a hydrogenated derivative of an aromatic modified terpene resin, a nonylphenol resin, Hydrogenated derivatives of indophenol resins, terpene resins (monoterpene, diterpene, triterpene, polyfluorene, etc.), terpene compounds such as hydrogenated terpene resins; aliphatic petroleum hydrocarbon resins (C5 based resins), aliphatic petroleum Hydrogenated derivative of hydrocarbon resin, aromatic petroleum hydrocarbon resin (C9 resin), hydrogenated derivative of aromatic petroleum hydrocarbon resin, dicyclopentadiene resin, hydrogenated derivative of dicyclopentadiene resin, C5/ A petroleum hydrocarbon compound such as a hydrogenated derivative of a C9 copolymer resin, a C5/C9 copolymer resin, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. These adhesion-imparting agents may be used alone or in combination of two or more.

The color of the adhesion-imparting agent is colorless to pale yellow, and it can also be used without substantial odor and heat. The liquid type adhesive with good stability imparts a resin.

Hereinafter, a preferred adhesion-imparting agent according to the use and performance will be more specifically described.

(adhesive imparting agent for hydrogenated derivatives)

The adhesion-imparting resin is preferably a hydrogenated derivative from the viewpoint of difficulty in coloring or low odor. The hydrogenated derivative is not particularly limited, and examples thereof include a hydrogenated derivative of a rosin resin, a hydrogenated derivative of a rosin ester, a hydrogenated derivative of an aromatic modified terpene resin, and a hydrogenated derivative of a nonylphenol resin; Hydrogenated derivative of petroleum hydrocarbon resin (C5 resin), hydrogenated derivative of aromatic petroleum hydrocarbon resin (C9 resin), hydrogenated derivative of dicyclopentadiene resin, modified dicyclopentadiene resin A hydrogenated derivative, a hydrogenated derivative of a C5/C9 copolymer resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. Among them, a hydrogenated derivative of an aromatic petroleum hydrocarbon resin (C9 resin) or a hydrogenated derivative of a dicyclopentadiene resin is preferable. The commercial product of such a hydrogenated derivative is not particularly limited, and examples thereof include Arkon P90, Arkon P100, Arkon P115, Arkon P125, Arkon P140 (trade name), Arkon M90, Arkon M100, and Arkon manufactured by Arakawa Chemical Co., Ltd. M115, Arkon M135 (trade name), Estergum H, Estergum HP (trade name), Haiperu (trade name), Regalite R1010 manufactured by Eastman Chemical Co., Regalite R1090, Regalite R1100, Regalite S5100, Regalite R7100, Regalite C6100 (trade name) ), Eastotac C100W, Eastotac C100L, Eastotac C100R, Eastotac C115W, Eastotac C115R (trade name), Staybelite E (trade name), Foral AXE (trade name), Staybelite Ester 10E (trade name), Clearon P manufactured by Yasuhara Chemical Co., Ltd. (trade name), Clearon M (trade name), Clearon K (trade name), YS POLYSTER UH (trade name), Escolez 5340 manufactured by Exxon, Escorez 5320, Escorez 5300, Escorez 5380, Escorez 5400, Escorez 227E, Escorez 5600, Escorez 5690 (trade name), Quintone A100, Quintone B170, Quintone M100 manufactured by ZEON, Japan Quintone R100, Quintone S195, Quintone D100, Quintone U185, Quintone DX395, Quintone 390N, Quintone N180, Quintone G100B, Quintone G115, Quintone E200SN, Quintone D200, Quintone 1105, Quintone 1325, Quintone 1340 (trade name), Idemitsu Kosei ( I-Marv S100, I-Marv S110, I-Marv P100, I-Marv P125, I-Marv P140 (trade name) manufactured by IDEMITSU), Rika Rosin F (trade name) manufactured by Rika Fine-Tech Co., Ltd., and the like.

(adhesive imparting agent other than hydrogenated derivatives)

The adhesion-imparting agent other than the hydrogenated derivative is not particularly limited, and examples thereof include natural rosin, polymerized rosin, modified rosin, glycerin of natural rosin, glycerin of modified rosin, and pentaerythritol ester of natural rosin, and modification. Rosin ester of rosin pentaerythritol ester, etc.; copolymer of natural terpene, terpolymer of natural terpene, aromatic modified terpene resin, indophenol resin, terpene resin; terpene resin, aliphatic petroleum A hydrocarbon resin (C5 resin), an aromatic petroleum hydrocarbon resin (C9 resin), a dicyclopentadiene resin, a C5/C9 copolymer resin, and a cyclic aliphatic petroleum hydrocarbon resin. Among them, aliphatic petroleum hydrocarbon resin (C5 system), aromatic petroleum hydrocarbon resin (C9 resin), C5/C9 copolymer resin, cyclic aliphatic petroleum hydrocarbon resin, terpene resin, natural and modified rosin are preferable. Esters and mixtures thereof. As a commercial item, Estergum AA-L, Estergum A, Estergum AAV, Estergum, Estergum 105, Estergum AT, Pencel A, Pencel AZ, Pencel C, Pencel D125, Pencel D160 (trade name) manufactured by Arakawa Chemical Co., Ltd. Super ester (trade name), Tamanol (trade name), Pinecrystal (trade name), Aradime (trade name), Wingtack10, Wingtack95, Wingtack98, WingtackExtra, WingtackRWT-7850, WingtackPLUS, WingtackET, WingtackSTS, Wingtack86 (CrayValley) Trade name), Norsolnene (product name), Piccotac 8095, Piccotac 1095, Piccotac 1098, Piccotac 1100 (trade name) manufactured by Eastman Chemical Co., Ltd., Exxon Mobil Escorez 1102, Escorez 1202, Escorez 1204LS, Escorez 1304, Escorez 1310, Escorez 1315, Escorez 224, Escorez 2101, Escorez 213, Escorez 807 (trade name), Sylvagum (trade name) and Sylvalite manufactured by Arizona Chemical Co., Ltd. (trade name), and Piccolyte (trade name) manufactured by Ashland, YS RESIN PX (trade name), YS RESIN PXN (trade name), YS POLYSTER U (trade name), YS POLYSTER T (trade name) manufactured by Yasuhara Chemical Co., Ltd. ), YS POLYSTER S (product name), YS POLYSTER G (product name), YS POLYSTER N (product name), YS POLYSTER K (trade name), YS POLYSTER TH (product name), YS RESIN TO (trade name), YS RESIN TR (trade name), YS RESIN SX (trade name), Marukarez M (trade name) manufactured by Maruzen Petrochemical Co., Ltd., etc.

(aliphatic adhesion-imparting agent)

From the viewpoint of obtaining an adhesive composition having high adhesion and high holding power and economy, it is preferred to use an aliphatic adhesion-imparting agent as the adhesion-imparting agent. The aliphatic-based adhesion-imparting agent is not particularly limited, and examples thereof include an aliphatic petroleum hydrocarbon resin (C5-based resin), a hydrogenated derivative of an aliphatic petroleum hydrocarbon resin (C5-based resin), and a C5/C9 copolymer resin. A hydrogenated derivative of a C5/C9 copolymer resin, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. In addition, the aliphatic-based adhesion-imparting agent means that the content of the aliphatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 88% by mass or more. Further, it is more preferably an adhesive imparting agent of 95% by mass or more. When the content of the aliphatic hydrocarbon group is within the above range, adhesion, retention, and economy tend to be further improved.

The aliphatic adhesion-imparting agent can be produced by polymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. The monomer having an aliphatic group and a polymerizable unsaturated group is not particularly limited, and examples thereof include natural and synthetic terpenes containing a C5 or C6 cyclopentyl group or a cyclohexyl group. Also, as other monomers that can be used in the copolymerization, there is no Particularly, for example, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2- Methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, terpene-phenol resin, and the like.

(Aromatic adhesion promoter)

From the viewpoint of obtaining an adhesive composition having high adhesion, high cohesive force, high coatability, or improving the balance between cohesive force and viscosity of the adhesive composition, it is preferably used as an adhesion-imparting agent. Aromatic adhesion promoter. The aromatic-based adhesion-imparting agent is not particularly limited, and examples thereof include an aromatic petroleum hydrocarbon resin (C9-based resin) and a C5/C9 copolymer-based resin. In addition, the aromatic-based adhesion-imparting agent means that the content of the aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 88% by mass. More preferably, it is more preferably 95% by mass or more of the adhesion-imparting agent. When the content of the aromatic hydrocarbon group is within the above range, the adhesion and the coating property tend to be further improved.

The aromatic-based adhesion-imparting agent can be produced by polymerizing or copolymerizing monomers each having an aromatic group and a polymerizable unsaturated group. The monomer having an aromatic group and a polymerizable unsaturated group is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, and tert-butyl group. Styrene, chlorostyrene, fluorene monomer (including methyl hydrazine). Further, the other monomer which can be used in the copolymerization is not particularly limited, and examples thereof include 1,3-butadiene, cis-1,3-pentadiene, and trans-1,3-pentadiene. 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, decene, decene-phenol resin, and the like. As a commercial item, Endex 155 (trade name), Kristalex 1120, Kristalex 3085, Kristalex 3100, Kristalex 5140, Kristalex F100 (trade name), Plascolyn 240, Plassolyn 290, Picotex 100 (trade name) manufactured by Eastman Chemical Co., Ltd. ), Nitto Resin Coumarone G-90, V-120, V-120S (trade name), etc.

(For the glass phase of the block copolymer (eg, polymer block (Ar)) and/or non-glass phase (for example, the block of the polymer block (D)) has an affinity adhesion-imparting agent)

As the adhesive composition, those having higher adhesion, lower change in strength or creep property (preferably smaller value), lower melt viscosity, higher heat resistance, and the like More preferably, it is a block containing a non-glass phase of the block copolymer contained in the adhesive composition (for example, a polymer block (D), usually a middle block, from the viewpoint of a well-balanced balance. An adhesive agent having an affinity of 20 to 75% by mass, and an adhesion-imparting agent having an affinity for a block of a glass phase of a block copolymer (for example, a polymer block (Ar), usually an outer block) 0.1 to 30% by mass. Here, the block copolymer includes the concepts of components (A) and (B).

The adhesion-imparting agent having an affinity for a block of the non-glass phase of the block copolymer (for example, the polymer block (D)) is not particularly limited, and examples thereof include a rosin-based compound, a terpene-based compound, and a fat. Group petroleum hydrocarbon resin (C5 resin), hydrogenated derivative of aliphatic petroleum hydrocarbon resin, C5/C9 copolymer resin, hydrogenated derivative of C5/C9 copolymer resin, cyclic aliphatic petroleum hydrocarbon resin, cyclic aliphatic Hydrogenated derivatives of petroleum hydrocarbon resins, and the like.

The content of the adhesion-imparting agent having an affinity for the non-glass phase of the block copolymer is preferably from 20 to 75% by mass, more preferably from 25 to 70% by mass, more preferably from 25 to 70% by mass, based on 100% by mass of the adhesive composition. It is 30 to 65 mass%.

The adhesion-imparting agent having an affinity for the block of the glass phase of the block copolymer (for example, the polymer block (Ar)) is not particularly limited, and for example, a resin having an aromatic ring in the molecule is preferable. The resin is not particularly limited, and examples thereof include an aromatic group-containing homopolymer or copolymer containing vinyl toluene, styrene, α-methylstyrene, saponin or oxime as a structural unit. Resin. Further, among these, Kristalex or Plascolyn, Picotex (manufactured by Eastman Chemical Co., Ltd., trade name) having α-methylstyrene, and the like are preferable.

The content of the adhesion-imparting agent having an affinity for the block of the glass phase of the block copolymer is preferably from 0.5 to 30% by mass, more preferably from 1 to 30% by mass, based on 100% by mass of the adhesive composition. 20% by mass, and more preferably 2 to 12% by mass.

From the viewpoint of obtaining an adhesive composition having a high initial adhesion, a high wettability, a low melt viscosity, or a high coating property, it is preferably used as an adhesion-imparting agent. A petroleum resin having an aromatic content of 3 to 12% by mass. The petroleum resin is not particularly limited, and examples thereof include an aliphatic petroleum hydrocarbon resin (C5 resin), a hydrogenated derivative of an aliphatic petroleum hydrocarbon resin (C5 resin), and an aromatic petroleum hydrocarbon resin (C9 resin). Hydrogenated derivative of aromatic petroleum hydrocarbon resin (C9 resin), dicyclopentadiene resin, hydrogenated derivative of dicyclopentadiene resin, C5/C9 copolymer resin, C5/C9 copolymer resin A hydrogenated derivative, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. The aromatic resin content of the petroleum resin is preferably from 3 to 12% by mass, more preferably from 4 to 10% by mass. Among them, hydrogenated petroleum resin is preferred.

From the viewpoint of obtaining an adhesive composition having a high initial adhesion, a high wettability, a low melt viscosity, or a high coating property, it is preferably used as an adhesion-imparting agent. Styrene oligomers. The styrene oligomer is not particularly limited, and examples thereof include an aromatic petroleum hydrocarbon resin (C9-based resin) such as Piccolastic A5 (trade name) or Piccolastic A75 (manufactured by Eastman Chemical Co., Ltd., trade name).

The content of the styrene oligomer is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less based on 100% by mass of the adhesive composition.

From the viewpoint of obtaining an adhesive composition having high low odor characteristics, high weather resistance, high transparency, colorlessness, low heat discoloration property, etc., as an adhesion-imparting agent, It is preferred to use a hydrogenated resin (for example, the above hydrogenated derivative).

The content of the adhesion-imparting agent is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 75 parts by mass or more based on 100 parts by mass of the hydrogenated block copolymer composition. In addition, the content of the adhesion-imparting agent is 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 350 parts by mass or less based on 100 parts by mass of the block copolymer composition. Moreover, the content of the adhesion-imparting agent is relative to 100 parts by mass of the block copolymer composition is 20 to 700 parts by mass, preferably 20 to 500 parts by mass, more preferably 30 to 400 parts by mass, still more preferably 50 to 350 parts by mass, and still more preferably 75 to 5 parts by mass. 350 parts by mass. When the content of the adhesion-imparting agent is within the above range, the adhesion characteristics are further improved.

In the case where the adhesive composition of the present embodiment contains a polymer other than the following components (A) and (B), the content of the adhesion-imparting agent is relative to the polymerization contained in the adhesive composition. The total amount of the particles is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 75 parts by mass or more. In addition, the content of the adhesion-imparting agent is 500 parts by mass or less, preferably 400 parts by mass or less, and more preferably 350 parts by mass or less based on 100 parts by mass of the total of the polymers contained in the adhesive composition. When the content of the adhesion-imparting agent is within the above range, the adhesion characteristics are further improved. The polymer contained in the adhesive composition herein means the component (A), the component (B), the following aromatic vinyl elastomer, the conjugated diene synthetic rubber, and the natural rubber.

(softener)

The term "softener" means a function of lowering the hardness of the adhesive composition and reducing the viscosity. The softening agent is not particularly limited, and examples thereof include known oils such as an alkane-based processing oil, a naphthenic processing oil, an aromatic processing oil, an extender oil, and the like. Lining oil; vegetable oil; plasticizer; synthetic liquid oligomer; and mixtures thereof.

Hereinafter, a preferred softener according to the use and performance will be more specifically described.

Oils can be used from the viewpoint of lowering the viscosity of the composition, improving the adhesion, and lowering the hardness. The oil is not particularly limited, and examples thereof include a known paraffin-based processing oil, a naphthenic processing oil, an aromatic processing oil, an extender oil, and the like. From the viewpoint of low-temperature characteristics, aging resistance, stain resistance, and color tone, the alkane-based processing oil is preferably an aromatic system from the viewpoint of compatibility. The processing oil is preferably a naphthenic processing oil from the viewpoint of a balance between low-temperature characteristics, aging resistance, stain resistance, color tone, and compatibility.

In the case where the adhesive composition is used as a percutaneous absorption preparation, it is preferred to use plastic in terms of improvement in transdermal absorbability and storage stability and improvement in drug solubility in the adhesive composition. The agent acts as a softener. The plasticizer is not particularly limited, and examples thereof include liquid paraffin, isopropyl myristate, ethyl laurate, and isopropyl palmitate, and a higher fatty acid having a carbon number of 12 to 16 and a carbon number of 1 to 4. Fatty acid ester of lower monohydric alcohol; fatty acid having 8-8 carbon atoms; glycol such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol; olive oil, castor oil , squalene, lanolin and other oils; ethyl acetate, ethanol, dimethyl hydrazide, fluorenylmethyl hydrazine, dimethyl hydrazine, dimethylformamide, dimethyl hydrazine An organic solvent such as amine, dimethyl laurylamine, dodecyl pyrrolidone, isosorbide, oleyl alcohol, lauric acid; liquid surfactant; ethoxylated stearyl alcohol, glyceride, meat Isotridecyl myristate, N-methylpyrrolidone, ethyl oleate, oleic acid, diisopropyl adipate, octyl palmitate, 1,3-propanediol, glycerol, and the like. Among these, a compound which is liquid at normal temperature is used. Among them, a glyceride is preferable, and a long-chain fatty acid triglyceride which is an ester of a fatty acid of 8 to 10 and glycerin is more preferable. Examples of the medium long chain fatty acid triglyceride include tris(octanoic acid/capric acid) glyceride. The plasticizers may be used alone or in combination of two or more.

In the case where the adhesive composition and the tape are used as a medical tape such as a tape, it is preferred to use a liquid paraffin in combination with other plasticizers.

When the adhesive composition and the adhesive tape are used for medical use, the amount of the plasticizer added is preferably from 3 to 30% by mass, more preferably from 3 to 20% by mass based on 100% by mass of the adhesive composition. %, further preferably 3 to 10% by mass. When the amount of the liquid plasticizer added is 3% by mass or more, the transdermal absorbability, storage stability, and drug solubility in the adhesive composition tend to be further improved. In addition, when the amount of the liquid plasticizer added is 20% by mass or less, the cohesive force of the adhesive composition tends to be further improved.

In the case where the adhesive composition is to be made softer, a synthetic liquid oligomer can be used from the viewpoint of improvement in exudation property. The synthetic liquid oligomer is sometimes referred to as a liquid rubber, and is not particularly limited, and examples thereof include a styrene oligomer, a butadiene oligomer, an isoprene oligomer, and a butene oligomer. Isobutylene oligomers, etc.

A vegetable oil is used in the case where a natural-derived component is to be used as a softening agent. The vegetable oil is not particularly limited, and examples thereof include castor oil, tall oil, and turpentine. From the viewpoint of cold resistance, castor oil is preferred.

The plasticizer is not particularly limited, and examples thereof include dibasic acid esters such as dibutyl phthalate (DBP) or dioctyl phthalate (DOP, Dioctyl Phthalate).

The commercial product of such a softening agent is not particularly limited, and examples thereof include Diana Fresia S32 manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-32, PW-90, PW-150, PS-430, Diana Process. Oil NP-24, NR-26, NR-68, NS-90S, NS-100, NM-280, Diana Process Oil AC-12, AC-640, AH-16, AH-24, AH-58 (trade name) ), White Oil Broom 350 (trade name) manufactured by Kukdong Oil & Chem Co., Ltd., DN Oil KP-68 (trade name), Enerper M1930 (trade name) manufactured by BP Chemicals Co., Ltd., Kaydol (trade name) manufactured by Crompton Co., Ltd., manufactured by Esso Corporation Primol352 (trade name), KN4010 (trade name) manufactured by PetroChina Company, Shentac N-40, N-60, N-70, N-75, N-80, Shintac PA-95, PA- manufactured by Kobe Oil Chemicals 100, PA-140, Shintac HA-10, HA-15, HA-30, HA-35 (trade name), JOMO Process P200, P300, P500, 750, JOMO Process R25, R50, R200, R1000 manufactured by Japan Energy , JOMO Process X50, X100E, X140 (trade name), Sunpar 110, 115, 120, 130, 150, 2100, 2280 manufactured by Japan Sun Oil, Sunthene oil 310, 410, 415, 420, 430, 450, 380, 480, 3125, 4130, 4240, JSO AROMA 790, Nitprene 720L (trade name), Fukkol manufactured by Fujitsu Process P-100, P-200, P-300, P-400, P-500, Fukkol Newflex 1060W, 1060E, 1150W, 1150E, 1400W, 1400E, 2040E, 2050N, Fukkol AROMAX 1, 3, 5, EXP1 (Commodity Name), Shellflex 371JY (trade name) manufactured by Shell in japan, Petrex Process oil PN-3, PN-3M, PN-3N-H (trade name), Petrex Process oil LPO-R, manufactured by Shanwen Oil Chemical Co., Ltd. LPO-V, PF-2 (trade name), COSMO Process 40, 40A, 40C, 200A, 100, 1000 (trade name) manufactured by COSMO OIL LUBRICANTS.

Further, the content of the softening agent is from 0 to 300 parts by mass, preferably from 10 to 175 parts by mass, more preferably from 20 to 150 parts by mass, per 100 parts by mass of the block copolymer composition. By setting the content of the softening agent within the above range, the adhesion characteristics can be further improved.

Further, the content of the softening agent is preferably 35% by mass or less, more preferably 3% by mass or more and 30% by mass or less based on the adhesive composition. By setting the content of the softening agent within the above range, the adhesion characteristics can be further improved.

Further, in the case where the adhesive composition of the present embodiment contains a polymer other than the following components (A) and (B), the content of the softener is relative to the polymer contained in the adhesive composition. The total amount is 100 parts by mass, preferably 0 to 300 parts by mass, preferably 10 to 175 parts by mass, more preferably 20 to 150 parts by mass. By setting the content of the softening agent within the above range, the adhesion characteristics can be further improved.

(other ingredients)

The adhesive composition of the present embodiment may contain a polymer other than the component (A) and the component (B), a wax, a polar group-containing polymer, a stabilizer, and a fine particle filler, as needed.

(polymers other than the component (A) and the component (B))

The polymer other than the component (A) and the component (B) is not particularly limited, and examples thereof include a polyolefin, a polyolefin-based copolymer, an aromatic vinyl-based elastomer, and other rubbers. In the present specification, the phrase "other than the component (A) and the component (B)" means any one of the component (A) and the component (B).

The content of the polymer other than the component (A) and the component (B) is not limited, and it is preferred that the total of the component (A) and the component (B) is relative to the component (A), the component (B), and the component (A). The total amount of the polymer other than the component (B) is 10 parts by mass or more. The total of the component (A) and the component (B) may be 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, or 80 parts by mass or more. It can also be 90 parts by mass or more. Further, a polymer other than the component (A) and the component (B) may not be contained.

The polyolefin or the polyolefin-based copolymer may be crystalline or non-crystalline, and may be present in combination, and is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, and 1-pentyl. Polymer of one or two or more kinds of monomers such as alkene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or a random polypropylene or ethylene-ethyl acrylate copolymer Things and so on. As a commercial product of polyolefin, VESTOPLAST 308, VESTOPLAST 408, VESTOPLAST 508, VESTOPLAST 520, VESTOPLAST 608, VESTOPLAST 703, VESTOPLAST 704, VESTOPLAST 708, VESTOPLAST 750, VESTOPLAST 751, VESTOPLAST 792, VESTOPLAST 828 manufactured by Degussa Co., Ltd. may be mentioned. VESTOPLAST 888, VESTOPLAST 891, VESTOPLAST EPNC702, VESTOPLAST EP807, VESTOPLAST 206, VESTOPLAST EP2403, VESTOPLAST 2412 (trade name), Licocene PP1302, Licocene PP1502, Licocene PP 1602, Licocene PP2602 (trade name) manufactured by Clariant Japan Co., Ltd., and the like.

The aromatic vinyl-based elastomer is not particularly limited, and examples thereof include a styrene-ethylene block copolymer, a styrene-butadiene block copolymer, and a styrene-propylene block copolymer. Styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene A polymer other than the component (A) and the component (B) such as an ethylenic block copolymer or a hydrogenated styrene-butadiene-isoprene block copolymer.

As a commercial item of a styrene-isoprene type block copolymer, Quintac 3421, Quintac 3620, Quintac 3433N, Quintac 3520, Quintac 3450, Quintac 3270, Quintac 3280, Quintac 3390 by the Japanese company. (trade name), D1107P, D1111, D1112P, D1113P, D1114PX, D1117P, D1119P, D1124P, D1128PX, D1193P, D4433P (trade name) manufactured by Kraton Polymers, Inc., VECTOR 4111A, VECTOR 4111N, VECTOR 4113A, VECTOR, manufactured by TSRC Corporation 4113N, VECTOR 4114A, VECTOR 4114N, VECTOR 4186A, VECTOR 4187A, VECTOR 4211A, VECTOR 4211N, VECTOR 4213A, VECTOR 4213N, VECTOR 4215A, VECTOR 4230, VECTOR 4293A, VECTOR 4411A (trade name), as styrene-butadiene Examples of commercially available block copolymers include D1101, D1102, D1116, D1118, D1122, D1133, D1144, D1184, D4141, D4150, and D4158 (trade names) manufactured by Kraton Polymers, Inc., VECTOR 2336 manufactured by TSRC Corporation. VECTOR 2411, VECTOR 2411P, VECTOR 2518, VECTOR 2518A, VECTOR 2518LD, VECTOR 2518P, VECTOR 2518PC, VECTOR, VECTOR 6241A , VECTOR 7400, VECTOR 8508, VECTOR 8508A, TAIPOL 3201, TAIPOL 3206, TAIPOL 4202, TAIPOL 4230, TAIPOL 4270 (trade name), Tufprene A, Tufprene 125, Tufprene 126S, Tufprene 315P, Asaprene T411, Asaprene, manufactured by Asahi Kasei Chemicals Co., Ltd. T412, Asaprene T413, Asaprene T420, Asaprene T432, Asaprene T436, Asaprene T437, Asaprene T438, Asaprene T439 (trade name), and the like. Examples of commercially available hydrogenated styrene-isoprene block copolymers include G1701, G1702, G1750X, G1765X, and G1780X (trade names) manufactured by Kraton Polymers, and Septon 1001 and Septon 1020 manufactured by Kuraray Co., Ltd. , Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104 (trade name), etc. Examples of the commercially available hydrogenated styrene-butadiene block copolymer include G1643, G1645, G1650, G1651, G1652, G1654, G1657, and G1726 (trade name) manufactured by Kraton Polymers Co., Ltd., manufactured by Kuraray Co., Ltd. Septon 8004, Septon 8006, Septon 8007, Septon 8076, Septon 8104 (trade name), TAIPOL 6150, TAIPOL 6151, TAIPOL 6152, TAIPOL 6154, TAIPOL 6159 (trade name) manufactured by TSRC, H1221, H1062 manufactured by Asahi Kasei Chemicals Co., Ltd. , H1052, H1041, H1051, H1057, H1043, N504 (trade name), and the like. The commercially available product of the hydrogenated styrene-butadiene-isoprene block copolymer may, for example, be Sepon 4033, Septon 4044, Septon 4055, Septon 4077, Septon 4099 (trade name) manufactured by Kuraray Co., Ltd., or the like.

Further, the content of the aromatic vinyl-based elastomer other than the component (A) and the component (B) is based on the block copolymer other than the component (A), the component (B), and the component (A) and the component (B). The total amount is 100 parts by mass, preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, still more preferably 15 to 85 parts by mass.

The other rubber is not particularly limited, and examples thereof include natural rubber; for example, isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-different Synthetic rubber of pentadiene rubber, propylene-butene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, and polypentene rubber. Among them, natural rubber is preferred from the viewpoint of crosslinkability or economy.

By using natural rubber, the cross-linking property of the adhesive composition is further improved, and the economy is also excellent.

In the case of containing natural rubber, the content thereof is preferably from 3 to 90% by mass, more preferably from 10 to 80% by mass, even more preferably from 15 to 75% by mass, based on 100% by mass of the adhesive composition. When the content of the natural rubber is within the above range, the crosslinkability, heat resistance, solvent resistance, and economy of the adhesive composition tend to be further improved.

Hereinafter, a polymer other than the preferred component (A) and component (B) depending on the use and performance Give a more specific explanation.

(Hydrogenated Aromatic Vinyl Elastomer)

The adhesion of the adhesive composition to the adherend, the reduction of the paste residue when peeled off, or the temporal change of the adhesive strength of the adhesive composition is suppressed or creeped (preferably, the value) A hydrogenated aromatic vinyl-based elastomer can be used from the viewpoint of being small, heat resistance, weather resistance, and the like. The hydrogenated aromatic vinyl-based elastomer is not particularly limited, and examples thereof include hydrogenated benzene having a structure such as S-EB-S (S: polystyrene block, EB: ethylene/butylene copolymer block). An ethylene-butadiene-based block copolymer; a hydrogenated styrene-isoprene block having a structure such as S-EP-S (S: polystyrene block, EP: ethylene/propylene copolymer block) Copolymer; hydrogenated styrene-butadiene-isoprene block copolymer having the structure of S-EEP-S (S: polystyrene block, EEP: ethylene/ethylene/propylene copolymer block) Wait. Among them, a hydrogenated styrene-butadiene block copolymer or a hydrogenated styrene-isoprene block copolymer is preferred.

The styrene content of the hydrogenated aromatic vinyl-based elastomer is preferably 10% by mass to 45% by mass, more preferably 13% by mass to 40% by mass, based on 100% by mass of the hydrogenated aromatic vinyl-based elastomer. Good is 15% by mass to 35% by mass.

In addition, the content of the polystyrene block of the hydrogenated aromatic vinyl-based elastomer is preferably 30% by mass or less, more preferably 21% by mass or less, and further preferably 21% by mass or less based on 100% by mass of the hydrogenated aromatic vinyl-based elastomer. Good is 15% by mass or less. When the content of the polystyrene block is within the above range, flexibility or compatibility tends to be further improved.

Further, the content of B in the ethylene/butene copolymer block in the hydrogenated aromatic vinyl-based elastomer is preferably high, and is preferably 35 mol% based on 100% by mass of the hydrogenated aromatic vinyl-based elastomer. The above is more preferably 45 mol% or more, further preferably 55 mol% or more, and particularly preferably 60 mol% or more. When the content of B in the ethylene/butene copolymer block is within the above range, flexibility or compatibility tends to be further improved.

Unsaturation of conjugated diene compounds in hydrogenated aromatic vinyl elastomers The hydrogenation rate of the double bond is preferably more than 90 mol%.

(Other partially hydrogenated aromatic vinyl elastomers)

From the viewpoint of the adhesion of the composition to the cohesive force, adhesion, viscosity, T (ODT) (regular to irregular transfer temperature), it is preferred to use other partially hydrogenated aromatic vinyl elastomer. The melt viscosity can be adjusted by adjusting T (ODT) (regular to irregular transfer temperature). The term "other partially hydrogenated aromatic vinyl elastomer" means a polymer block mainly comprising a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, conjugated The hydrogenation rate H (%) of the ethylenic compound based on the unsaturated double bond is 5 to 90 mol%, and the maximum value of the loss coefficient tan δ of -100 ° C to 0 ° C is less than 0.4.

(non-hydrogenated aromatic vinyl elastomer)

As the adhesive composition, a non-hydrogenated aromatic vinyl group can also be used because of its high flexibility, high adhesion, suppression of gelation, or high economical efficiency. Elastomer. The non-hydrogenated aromatic vinyl-based elastomer is not particularly limited, and examples thereof include a styrene-ethylene block copolymer, and SBS and (SB) _n X (S: polystyrene block, B: poly a styrene-butadiene block copolymer having a structure such as a butadiene block, X: a residue of a coupling agent; a styrene-propylene block copolymer; having SIS, (SI) _n X (S: a styrene-isoprene block copolymer having a structure of polystyrene block, I: polyisoprene block, X: a residue of a coupling agent; having (S-(I/B)) _n X, S-(I/B)-S (S: polystyrene block, I/B: isoprene/butadiene copolymer block (isoprene and butadiene can be alternated in any ratio A styrene-butadiene-isoprene block copolymer having a structure in which the ratio may not be fixed, X: a residue of a coupling agent). Among them, (SI) _n X, (SB) _n X, (S-(I/B)) _n X is preferable, and it is more preferable to have a radial structure. These may be used alone or in combination of two or more.

The styrene content of the non-hydrogenated aromatic vinyl elastomer is preferably 45% by mass or less based on 100% by mass of the non-hydrogenated aromatic vinyl elastomer.

Further, the content of the diblock (for example, SB or SI, SBX, SIX) of the non-hydrogenated aromatic vinyl elastomer is preferably 10 to 80% by mass based on 100% by mass of the non-hydrogenated aromatic vinyl elastomer. %.

(isoprene block copolymer)

As the adhesive composition, an isoprene-based block copolymer having a non-hydrogenated isoprene monomer unit can also be used from the viewpoint of having excellent viscosity or economical viewpoint. The isoprene-based block copolymer is not particularly limited, and for example, it is preferably (SI)n, (SI)nS, (SI)nX (S: polystyrene block, I: polyisoprene) A styrene-isoprene block copolymer having a structure of n: an integer of 1 or more, preferably an integer of 1 to 6, and a residue of X: a coupling agent. These may be used alone or in combination of two or more.

The styrene content of the isoprene-based block copolymer is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass based on 100% by mass of the isoprene-based block copolymer. % or less, more preferably 18% by mass or less.

(conjugated diene synthetic rubber)

A conjugated diene-based synthetic rubber can be used from the viewpoint of workability, low melt viscosity at 180 ° C or lower, good adhesion or adhesion, adhesion, and cutability. The conjugated diene-based synthetic rubber is not particularly limited, and examples thereof include isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, and styrene- Isoprene rubber, propylene-butene rubber, and the like.

Further, as the adhesive composition for a tape, a polybutadiene rubber or a polyisoprene rubber can be used from the viewpoint of improving the adhesion to the back surface or the skin adhesion. Among them, polyisoprene rubber is more preferred. The amount of the polybutadiene rubber and the polyisoprene rubber added is preferably from 3 to 25% by mass, more preferably from 5 to 20% by mass, even more preferably from 5 to 20% by mass, based on 100% by mass of the adhesive composition. 15% by mass. When the addition amount of the polybutadiene rubber and the polyisoprene rubber is 3% by mass or more, there is a tendency to adhere from the back surface to the skin and the skin adhesion force. The tendency to step up. In addition, when the addition amount of the polybutadiene rubber and the polyisoprene rubber is 25% by mass or less, the cohesive force is further improved, and the paste residue tends to be suppressed.

As the conjugated diene-based synthetic rubber, a conjugated diene system can also be used from the viewpoints of workability of the adhesive composition, low melt viscosity at 180 ° C or lower, good adhesion or adhesion, and adhesion. Diblock copolymer. The conjugated diene-based diblock copolymer is not particularly limited, and examples thereof include a polymer having a structure such as S-I, (S-I)X, S-B, or (S-B)X, and the like. These may be used alone or in combination of two or more. They may be liquid or solid at normal temperature.

The content of the conjugated diene-based synthetic rubber is preferably from 3 to 90% by mass, more preferably from 10 to 80% by mass, even more preferably from 15 to 75% by mass, based on 100% by mass of the adhesive composition. When the content of the conjugated diene-based synthetic rubber is within the above range, the oil repellency, low melt viscosity, viscosity, adhesion, adhesion, and flexibility of the adhesive composition tend to be further improved.

(ion polymer)

As the adhesive composition, when a high low-temperature coating property, a low creep property, a high strength, or a high elongation is required, the polymer can be used in the state of an ionic polymer. The ionic polymer is not particularly limited, and for example, a homopolymer or a copolymer of a carboxylate, a sulfonate or a phosphonate which is neutralized or partially neutralized by a metal ion is preferably contained. The content of the ionic polymer is preferably 5% by mass or less based on the total amount of the adhesive composition.

(polyolefin resin)

The adhesive composition has a high-temperature storage stability or a high elongation, or reduces the amount of the adhesive-imparting resin in the adhesive composition (55 mass% or less, and further 45 mass% or less in the composition) A polyolefin-based resin can be used from the viewpoints of improvement in high fluidity, fluidity, adhesion characteristics, economy, and the like. The polyolefin-based resin is not particularly limited, and for example, it is preferred to use a copolymer of an α-olefin and an olefin or a propylene. Polymer. The melting point of the polymer (condition: DSC measurement, 5 ° C / min) is preferably 110 ° C or lower, more preferably 100 ° C or lower, further preferably 60 ° C to 90 ° C. The polymers may be either resins or elastomers. The commercially available product of the polyolefin-based elastomer is not particularly limited, and examples thereof include AFFINITY and AFFINITY GA (trade name) manufactured by DOW Chemical Co., Ltd., and Vistamaxx (trade name) manufactured by ExxonMobil Chemical Co., Ltd., and the like, and are not particularly limited. Preferred are AFFINITY GA1875, GA1900, GA1000R, GA1950, EG8185, EG8200G, PL1280G, and the like.

Further, from the viewpoint of creep properties (preferably, the value is small), it is more preferable to have a block olefin-based elastomer. The molecular weight distribution of the polymers is preferably from 1 to 4, more preferably from 1 to 3. Further, from the viewpoint of workability, it is more preferred to use two or more of these polymers in combination. Specifically, it is preferred to use a polymer of 30,000 to 60,000 and 60,000 to 90,000 in combination, more preferably at least 3,5000 to 5,5000 and 60,000 to 80,000.

(liquid component)

It is preferred to contain a liquid component (oil or the like) in the adhesive composition using a polyolefin resin. The content of the liquid component is preferably 20% by mass or more, and more preferably 25% by mass or more based on 100% by mass of the adhesive composition. Further, when an elongation is required, it is preferred to use an olefin-based elastomer in combination, and it is more preferably used for an olefin-based elastomer having a Tg of -10 ° C or lower.

(wax)

A wax may be contained in the adhesive composition as needed. The amount of the wax added is preferably 20% by mass or less, more preferably 2 to 10% by mass, still more preferably 5 to 10% by mass based on 100% by mass of the adhesive composition. When the amount of the wax added is within the above range, the melt viscosity is increased, and in particular, the melt viscosity at 140 ° C or lower tends to decrease.

The wax is not particularly limited, and examples thereof include paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. By using such a wax, there is a tendency that the melt viscosity, especially the melt viscosity at 140 ° C or lower, is further lowered.

The melting point of the wax is preferably 50 ° C or higher, more preferably 65 ° C or higher, further preferably 70 ° C or higher, and still more preferably 75 ° C or higher. Further, the melting point of the wax is preferably 110 ° C or lower. When the melting point of the wax is within the above range, there is a tendency that the melt viscosity, especially the melt viscosity at 140 ° C or lower, is further lowered.

Further, the softening point of the adhesion-imparting agent to be used in combination with the wax is preferably 70 ° C or higher, more preferably 80 ° C or higher. In the adhesive composition obtained in this case, G' (measurement conditions: 25 ° C, 10 rad/s) is preferably 1 MPa or less, and the crystallization temperature is preferably 7 ° C or less.

As a commercially available product, the product name "115", the product name "120", the product name "125", the product name "130", and the product name "135", which are manufactured by Nippon Seiko Co., Ltd., may be mentioned. Product name "140", product name "150", product name "155", product name "HNP-3", product name "HNP-5", product name "HNP-9", product name "HNP-10", Product name "HNP-11", product name "HNP-12", product name "HNP-51", product name "SP-0145", product name "SP-0160", product name "SP-0165", product name "SP-1035", product name "SP-1040", product name "SP-3035", product name "SP-3040", product name "EMW-0001", product name "EMW-0003", product name "Hi -Mic-1045", trade name "Hi-Mic-1070", trade name "Hi-Mic-1080", trade name "Hi-Mic-1090", trade name "Hi-Mic-2045", trade name "Hi -Mic-2065", the trade name "Hi-Mic-2095", "Ultrathene 7A55A" manufactured by Tosoh, the trade name "A-C540" manufactured by Honeywell, the trade name "A-C540A", and the trade name "A- C580", the trade name "A- C5120", trade name "A-C400", trade name "A-C400A", trade name "A-C405 (S)", trade name "A-C405 (M)", trade name "A-C405 (T) "The product name is "A-C645P", the product name is "A-C573A", and the product name is "A-C573P".

(Polymer-containing polymer)

The adhesive composition may optionally contain a polar group-containing polymer containing an atom selected from the group consisting of nitrogen, oxygen, helium, phosphorus, sulfur, tin, and the like. As a polar group The polymer is not particularly limited, and examples thereof include a so-called modified polymer bonded to a block copolymer or a modified block in which a block copolymer component is modified with a modifier such as maleic anhydride. A copolymer or an oil obtained by modifying a side chain or a terminal with an amine or an epoxy, a carboxylic acid, a carboxylic acid anhydride or the like. By using a polymer containing a polar group, there are resins having a high SP value such as a superabsorbent polymer (SAP), an acrylic resin, a resin such as vinyl chloride or nylon, or a crosslinked product thereof, and glass or metal. The adhesive properties of the adhesive are further improved. HG252 (trade name) manufactured by Kuraray Co., Ltd., M1943, M1911, M1913, MP10, Tufprene 912 (trade name) manufactured by Asahi Kasei Chemicals Co., Ltd., and TAIPOL 7131 (trade name) manufactured by TSRC Co., Ltd., and the like are exemplified.

(stabilizer)

The adhesive composition may contain a stabilizer as needed. The term "stabilizer" refers to the prevention of the decrease in molecular weight due to the heat of the hot-melt adhesive, gelation, coloration, odor generation, etc., and is not particularly special for the purpose of improving the stability of the hot-melt adhesive. limit.

Examples of the stabilizer include an antioxidant, a light stabilizer, and the like. The antioxidant and the light stabilizer are usually used in a disposable product, and are not particularly limited as long as they are disposable products which can achieve the following objectives.

(Antioxidants)

The "antioxidant" can be used, for example, to prevent oxidative degradation of the hot melt adhesive. The antioxidant is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol and 3-(4'-hydroxy-3',5'-di-t-butylphenyl group. n-Octadecyl propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6 -T-butylphenol), 2,4-bis[(octylthio)methyl]o-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-acrylate Methylbenzyl)-4-methylphenyl ester, 2,4-di-p-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]benzene a phenolic antioxidant such as an ester or 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl) acrylate; dilauryl thiodipropionate, lauryl thiodipropionate a sulfur-based antioxidant such as a lipid ester or pentaerythritol tetrakis(β-laurylthiopropionate); A phosphorus-based antioxidant such as (nonylphenyl) ester or tris(2,4-di-tert-butylphenyl)phosphite. These may be used alone or in combination of two or more.

Specific examples of the commercial product of the antioxidants include Sumilizer GM (trade name) manufactured by Sumitomo Chemical Industries Co., Ltd., Sumilizer TPD (trade name), and Sumilizer TPS (trade name), and Irganox manufactured by Ciba Specialty Chemicals Co., Ltd. 1076 (trade name), Irganox 1010 (trade name), Irganox HP2225FF (trade name), Irgafos 168 (trade name), and Irganox 1520 (trade name), JF77 (trade name) manufactured by Seongbuk Chemical Co., Ltd.

The content of the antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less based on 100 parts by mass of the adhesive composition.

(light stabilizer)

The "light stabilizer" can be used, for example, to improve the light resistance of the hot melt adhesive (lower adhesion characteristics after UV irradiation). The light stabilizer is not particularly limited, and examples thereof include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'- a benzotriazole-based ultraviolet absorber such as tributylphenyl)benzotriazole or 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole a benzophenone-based ultraviolet absorber such as 2-hydroxy-4-methoxybenzophenone; A UV absorber; a hindered amine light stabilizer; a lactone stabilizer: a hindered amine light stabilizer (HALS, Hindered Amine Light Stabilizer). These may be used alone or in combination of two or more.

Specific examples of the commercial product of the light stabilizer include TINUVIN P (trade name) manufactured by BASF, TINUVIN 770DF (trade name), Cimassorb 2020 FDL (trade name), and Adekastab LA-52 (trade name) manufactured by ADEKA Corporation. ), Adekastab LA-57 (trade name), Adekastab LA-77Y (trade name).

The content of the light stabilizer in the adhesive composition of the present embodiment is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.07% by mass or more in terms of high light resistance. .

In addition, the light stabilizer content in the adhesive composition of the present embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, in terms of suppression of the bleeding of the light stabilizer or economic efficiency. It is preferably 0.3% by mass or less.

In terms of higher light resistance, it is preferred to further use the above antioxidant in combination with the above-mentioned light stabilizer.

Among the antioxidants, in terms of higher light resistance, it is preferred to use at least a phosphorus-based antioxidant in addition to the above-mentioned light-resistant agent.

The content of the antioxidant in the adhesive composition of the present embodiment is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, and still more preferably 0.06% by mass or more in terms of high light resistance.

In addition, the light stabilizer content in the adhesive composition of the present embodiment is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less in terms of suppression of oxidation of the antioxidant or economy.

(microparticle filler)

The adhesive composition may contain a particulate filler as needed. The fine particle filler is not particularly limited, and examples thereof include mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, zinc white, and active zinc white. Light magnesium carbonate, barium hydroxide gel, diatomaceous earth, barium sulfate, and the like. The shape is preferably spherical, and the size thereof (the diameter in the case of a spherical shape) is not particularly limited.

[Characteristics of adhesive composition]

The properties of the adhesive composition of the present embodiment can be measured by using the tapes produced according to the conditions shown in the following examples, depending on the measurement conditions shown in the examples.

G' (measurement condition: 25 ° C, 10 rad/s) of the adhesive composition is preferably 20,000 or less, more preferably 15,000 or less. When the G' of the adhesive is within the above range, the paste residue of the adhesive composition tends to be further reduced.

Further, the content of the liquid diluent is preferably 100% by mass based on the adhesive composition. It is 60% by mass or less. By using the content of the liquid diluent within the above range, it is particularly useful for skin application including an adhesive for transdermal drug delivery.

The adhesive composition of the present embodiment can also be used for paper processing, binding, disposable products, and the like. Among them, since it is excellent in a wet state, it is suitable for a disposable product. The disposable product can be selected from the group consisting of woven fabrics, non-woven fabrics, rubber, resins, papers, polyolefin films, polyester films, polyvinyl chloride (PVC, PolyVinyl Chloride) films, ionic polymer films, polyvinylidene chloride (PVDC, Poly(vinylidene chloride)) film, polyvinyl alcohol (PVA, Polyvinyl alcohol) film, polycarbonate (PC, Polycarbonate) film, polystyrene (PS, Polystyrene) film, polyacrylonitrile (PAN, Polyacrylonitrile) Film, polyethylene naphthalate (PEN) film, cellophane film, nylon film, polyimide film, ethylene-methacrylic acid copolymer (EMAA, Ethylene methyacrylic acid copolymer) film, ethylene - At least one of the members consisting of the ethylene glycol copolymer (EVOH) film is formed by solution coating or hot melt coating of the adhesive composition. Further, the polyolefin film is preferably a polyethylene film or a polypropylene film for reasons such as durability and cost. Further, the paper is preferably kraft paper or Daolin paper for reasons of durability and cost, and is preferably a kraft paper obtained by laminating polyethylene from the viewpoint of durability and water resistance.

The melt viscosity of the hot-melt adhesive for disposable materials of sanitary materials at 150 ° C is preferably 5,000 mPa·s or less, more preferably 400 to 3,500 mPa·s, and still more preferably 800 to 3,000 mPa·s. The melt viscosity refers to the viscosity of the melt of the hot-melt adhesive, and can be measured by a cloth type RVT type viscometer (spindle No. 27). By setting the melt viscosity to the above range, the hot-melt adhesive is suitable for low-temperature coating, and can be uniformly applied to a non-woven fabric to be easily impregnated, and is therefore suitable for disposable products suitable for sanitary materials.

The disposable product suitable for a sanitary material is not particularly limited, and examples thereof include a disposable diaper, a sanitary napkin, a pet pad, a hospital gown, and a surgical white gown.

[Method for Producing Adhesive Composition]

The adhesive composition of the present embodiment can be produced by mixing the above hydrogenated block copolymer composition, an adhesion-imparting agent, a softening agent, and other components as needed, by a known method. The mixing method is not particularly limited, and examples thereof include a method in which a block copolymer composition, an adhesion-imparting agent, and a softener are uniformly mixed while being heated by a mixer or a kneader.

The temperature at the time of mixing is preferably from 130 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C, and still more preferably from 150 ° C to 200 ° C. When the temperature at the time of mixing is 130 ° C or more, the block copolymer composition can be sufficiently melted to make the dispersion favorable. In addition, when the temperature at the time of mixing is 220 ° C or lower, the evaporation of the low molecular weight component of the crosslinking agent or the adhesion-imparting agent and the deterioration of the adhesion characteristics tend to be prevented.

[Coating method of adhesive composition]

In the case where the adhesive composition is applied, the coating method is not particularly limited as long as the target product can be obtained, and for example, a solution in which the adhesive composition is dissolved in a solvent is used. A method of coating or a method of coating by a hot melt coating method in which an adhesive composition is melted and applied.

Among them, in terms of environmental pollution or ease of coating, a hot melt coating method is preferred. The hot melt coating method is roughly classified into contact coating and non-contact coating. The term "contact coating" refers to a coating method in which a sprayer is brought into contact with a member or a film when a hot melt adhesive is applied. Moreover, "non-contact coating" means a coating method in which the discharger is not in contact with the member or the film when the hot-melt adhesive is applied. The contact coating method is not particularly limited, and examples thereof include slit coating, roll coating, die coating, porous coating by a porous coating, and pattern coating. Further, the non-contact coating method is not particularly limited, and examples thereof include spiral coating which can apply a coating agent in a spiral shape in air, or can be applied as a corrugated omega coating. Or control slit coating, can be applied as a flat slit spray coating or curtain spray coating, can be applied as a dot-like dot coating, can be applied as a linear droplet coating, Foaming melt coating of hot melt foaming, coating to a linear form, spray coating by mist application Cloth and so on.

Previous hot melt adhesives lacking thermal stability are prone to phase separation of components in high temperature baths. Phase separation also causes blockage of the tank filter and the transfer piping. In this regard, the adhesive composition of the present embodiment has good thermal stability and is uniformly melted in a high temperature bath of 100 to 220 ° C to suppress phase separation.

In a manufacturing line for disposable articles suitable for sanitary materials, hot melt adhesives are typically applied to various components of the disposable article, such as toilet paper, cotton, nonwovens, polyolefin films, and the like. At the time of coating, the hot melt adhesive can be used by ejecting from various extruders.

Hot melt adhesives for disposable articles suitable for sanitary materials are suitable for spiral coating. Since the hot melt adhesive can be applied in a wide range by spray coating, it is extremely useful in the manufacture of disposable articles. The hot-melt adhesive that can be applied over a wide range can narrow the coating range by adjusting the pressure of the hot gas.

If the hot melt adhesive is difficult to apply in a wide range, a large number of spray nozzles are required in order to obtain a sufficient joint area, and it is not suitable for manufacturing a disposable product such as a urine collecting liner, and a complicated shape is discarded. Products. In this regard, the adhesive composition of the present embodiment can be spirally coated over a wide range, and thus can be preferably used as a disposable product suitable for sanitary materials.

Since the adhesive composition of the present embodiment has good coating suitability at 150 ° C or lower, it is useful for the production of a disposable product suitable for sanitary materials. If the hot melt adhesive is applied at a high temperature, the polyolefin (preferably polyethylene) film as a substrate of the disposable product is melted or thermally shrunk, so that the appearance of the disposable product is greatly impaired. When the hot-melt adhesive is applied at 150 ° C or lower, the appearance of the polyolefin (preferably polyethylene) film or the non-woven fabric as the substrate of the disposable product is hardly changed, and the appearance of the product is not impaired.

The adhesive composition of the present embodiment is excellent in high-speed coating suitability, and is therefore suitable for use in a disposable product suitable for sanitary materials in a short period of time. When a hot-melt adhesive is applied to a substrate that is transported at a high speed, there is a case where a contact coating method is used. The material is broken due to friction. The adhesive composition of the present embodiment is suitable as a spiral coating for one type of non-contact coating, and is therefore suitable for high-speed coating, and can improve the production efficiency of the disposable product. Further, the adhesive composition of the present embodiment suitable for high-speed coating does not cause confusion in the coating pattern.

<Adhesive tape, method of manufacturing label>

The method for producing the adhesive composition of the present embodiment is not particularly limited, and examples thereof include a known mixer, a kneader, a uniaxial extruder, a twin screw extruder, and a Banbury mixer. A method in which a hydrogenated block copolymer, an adhesion-imparting resin, and optionally other block copolymers and oils are heated while being uniformly mixed at a specific blending ratio.

The adhesive composition of the present embodiment is preferably used by laminating at least a substrate. The type of the substrate is not limited, and for example, a film containing a thermoplastic resin or a non-thermoplastic substrate such as paper, metal, woven fabric, or nonwoven fabric may be used.

In the case of using a masking material at the time of replacement coating operation of a coating material, it is preferable to use a metal foil such as an aluminum foil as a substrate from the viewpoint of suppressing corrosion of the chemical solution.

Moreover, when it is used for a sanitary article, a nonwoven fabric can be used as a base material, and a stretchable laminated body in which an adhesive composition layer and an elastomer layer are sequentially laminated on a nonwoven fabric can be used. In order to exhibit excellent conformability, it is preferable that the strength residual ratio at the 100% elongation of the stretchable laminate is 80% or more and the strength residual ratio at 70% elongation is 70% or more.

A release agent or a release agent may be added to the material of the substrate. Examples of the release agent include a long-chain alkyl-based release agent and an oxime-based release agent. A release layer may be further provided in addition to the substrate.

In the case where higher weather resistance (lower adhesion change after UV irradiation) is required, it is more preferable to use a substrate or a release layer having a low ultraviolet transmittance, and it is more preferable that the transmittance is 1% or less.

Further, from the viewpoint of suppressing oxidative degradation due to UV irradiation, it is preferred to use a substrate having a low oxygen permeability coefficient or a release layer, preferably having an oxygen permeability coefficient of 10,000 at 20 ° C under dry conditions. ‧20 μm/m ² ‧day‧atm) or less, more preferably 1,000 (cc‧20 μm/m ² ‧day‧atm) or less, further preferably 500 (cc‧20 μ/m ² ‧day‧atm) or less

The method of applying the adhesive composition of the present embodiment to a substrate is not particularly limited, and examples thereof include a T-die coating method, a roll coating method, a multi-drop coating method, and a spray coating. Bufa and so on. Further, any of the extrusion coating (hot melt coating) method or the melt coating method may be used, but the adhesive composition of the present embodiment is suitable for extrusion coating having high heat aging resistance and high economy. Bufa.

[use]

The adhesive composition of the present embodiment has excellent solubility, coating properties, discharge stability, surface muscle, adhesion, and adhesion, and the adhesion balance characteristics are also good. By utilizing this feature, it can be used in various tapes, labels, pressure-sensitive sheets, pressure-sensitive sheets, surface protection sheets, films, various light plastic molded products for fixing pastes, carpet fixing pastes, and tiles. Fixing paste, adhesive, etc., especially for adhesive tape, adhesive sheet, film, adhesive label, surface protection sheet, film, and eutectic. For use.

[Examples]

Hereinafter, the present invention will be specifically described by way of specific examples and comparative examples, but the present invention is not limited to the following examples. Further, in the following examples and comparative examples, the measurement of the properties or physical properties of the polymer was carried out by the following method.

[(1): Characteristics of hydrogenated block copolymer]

<(1-1) Weight average molecular weight>

The weight average molecular weight of the hydrogenated block copolymer is determined using a calibration curve obtained by measurement from a commercially available standard polystyrene (made using the peak molecular weight of standard polystyrene) based on the molecular weight of the peak of the chromatogram. . As a hydrogenated block copolymer, it contains In the case of the hydrogenated block copolymer having two different structures of the component (A) and the component (B), the peak having the smallest weight average molecular weight is taken as the component (A), which is second only to the weight average molecular weight of the component (A). The larger peak was obtained as the component (B) in the same manner. Further, the component (A) and the component (B) are divided by the peak area of each component by the total peak area ((the peak area of the component (A) or the component (B)) / (total peak area)) is 0.1. the above. As a measurement software, it was collected using HLC-8320EcoSEC, and analyzed as an analysis software using HLC-8320. The peak area was measured by the following method.

(measurement conditions)

GPC: HLC-8320GPC (manufactured by Tosoh Co., Ltd.)

Detector: RI

Detection sensitivity: 3mV/min

Sampling pitch; 600msec

Pipe column: TSKgel superHZM-N (6mm I.D×15cm) 4 pieces (manufactured by Tosoh Co., Ltd.)

Solvent: tetrahydrofuran (THF, Tetrahydrofuran)

Flow rate: 0.6mm/min

Concentration: 0.5mg/mL

Column temperature: 40 ° C

Injection volume: 20μL

<(1-2) Content of vinyl aromatic hydrocarbon monomer unit (styrene)>

A certain amount of the hydrogenated block copolymer was dissolved in chloroform, and the absorption wavelength of the vinyl aromatic compound component (styrene) in the solution was measured using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation). Peak intensity of 262 nm). The content of the vinyl aromatic hydrocarbon monomer unit (styrene) was calculated from the obtained peak intensity using a calibration curve.

<(1-3) Amount of ethylene bond in the conjugated diene monomer unit and hydrogenation ratio of the conjugated diene monomer unit>

By adding a large amount of methanol to the reaction liquid after the hydrogenation reaction, the hydrogenation is carried out. The block copolymer and the hydrogenated block copolymer are precipitated and recovered. Then, the hydrogenated block copolymer was extracted with acetone, and the hydrogenated block copolymer was vacuum dried. This was used as a sample for 1 H-NMR measurement, and the hydrogenation rate and the amount of ethylene bond were measured. The conditions of 1 H-NMR measurement are as follows.

(measurement conditions)

Measuring machine: JNM-LA400 (manufactured by JEOL)

Solvent: deuterated chloroform

Determination of samples: extracts before and after hydrogenation of the polymer

Sample concentration: 50mg/mL

Observation frequency: 400MHz

Chemical shift reference: TMS (tetramethyl decane)

Pulse delay: 2.904 seconds

Number of scans: 64 times

Pulse width: 45°

Measuring temperature: 26 ° C

<(1-4) Average molecular weight of polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit>

The average molecular weight of the polymer block (Ar) is determined by the following formula using the weight average molecular weight of the hydrogenated block copolymer and the content (% by mass) of the polymer block (Ar) in the hydrogenated block copolymer. .

(weight average molecular weight of hydrogenated block copolymer) × (average content (% by mass) of polymer block (Ar) in hydrogenated block copolymer) / 100 = (based on vinyl aromatic hydrocarbon monomer unit Average molecular weight of the polymer block (Ar)

The "average content (% by mass) of the polymer block (Ar) in the hydrogenated block copolymer" is the case when the polymer block (Ar) contained in the hydrogenated block copolymer is one. The content of the segments is the average content of the blocks when the polymer block (Ar) is two or more. Average content (% by mass) of the polymer block (Ar) in the hydrogenated block copolymer The number of the polymer block (Ar) mainly composed of the vinyl aromatic hydrocarbon monomer unit and the number of the vinyl aromatic hydrocarbon monomer units which are contained in the hydrogenated block copolymer can be calculated by the following method.

(Average content (% by mass) of the polymer block (Ar) in the hydrogenated block copolymer) = (content (mass fraction) of the vinyl aromatic hydrocarbon monomer unit of the hydrogenated block copolymer) (Number of polymer blocks (Ar) mainly composed of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer)

(In addition, in the case where the hydrogenated block copolymer contains the component (A) and the component (B), the value calculated by the above method using the weight average molecular weight of each component)

<(1-5) Content of component (A) and component (B)>

In the case where the hydrogenated block copolymer contains a hydrogenated block copolymer having two different structures of the component (A) and the component (B), the peak area of the component (A) is relative to the above (1-1) The ratio of the total peak area of the dissolution curve measured in the middle is taken as the content of the component (A). Further, the ratio of the peak area of the component (B) to the total peak area of the elution curve measured in the above (1-1) is defined as the content of the component (B). Furthermore, regarding the area ratio, the analysis using the HLC-8320 in the analysis software was obtained by vertical division under the inflection point of the curve between the peaks.

<(2): Method for Measuring Physical Properties of Hydrogenated Block Copolymer Compositions Obtained in Production Examples> <(2-1) Determination of metal compound (metal amount) in terms of metal atom>

The amount of the metal contained in the hydrogenated block copolymer composition obtained in the following production example was measured using an inductively coupled plasma (ICP, Inductivuty Coupled Plasa, manufactured by Shimadzu Corporation, device name: ICPS-7510). First, the hydrogenated block copolymer is completely dissolved by sulfuric acid and nitric acid, and an aqueous solution containing a metal component is sprayed into an argon plasma to measure the intensity of the wavelength of light inherent to various metal elements emitted therefrom, by a calibration curve. The amount of the metal contained in 100 parts by mass of the hydrogenated block copolymer composition was determined.

<(2-2) Determination of particle size (particle size distribution)>

The particle diameter of the metal compound particles contained in the hydrogenated block copolymer composition obtained in the following production examples was measured by the following method by a laser diffraction type particle size distribution meter (manufactured by HORIBA Co., Ltd., LA-300).

The cyclohexane solution of the hydrogenated block copolymer composition was dropped into a circulating bath in which cyclohexane was circulated, and the cycle concentration of the region in which the transmittance was 70 to 98% was controlled, and the particle diameter was measured under the following conditions.

In the case where the hydrogenated block copolymer composition contains a metal other than the titanium compound, the average particle diameter obtained by the following method is a particle diameter of the entire metal compound particles of the titanium compound and the other metal compound.

[Measurement conditions]

Measurement method: Mie scattering theory

Measuring range: 0.1~600μm

Measurement time: 20sec

Light source: 650nm semiconductor laser 5mW

Number of data reads: 5~10 times

Measuring temperature: 25 ° C

Here, the average particle diameter refers to an arithmetic mean diameter, and is a value obtained by arithmetically averaging a frequency distribution, and is represented by the following formula.

Arithmetic mean diameter = Σ{q(J)×X(J)}÷Σ{q(J)}

J: particle size division number

q(J): frequency distribution value (%)

X(J): representative value of the particle size range of the Jth (μm)

Further, the content of the titanium compound having a particle diameter of 0.1 μm to 50 μm in the titanium compound, the content of the titanium compound having a particle diameter of 0.1 μm to 100 μm, and the average particle diameter of the titanium compound are passed through the LA-300 soft body. Partially accumulating.

<(2-3) Analysis of the state of the metal component in the hydrogenated block copolymer composition>

X-ray diffraction device XRD (Ultra-IV (Cu bulb) manufactured by Rigaku Co., Ltd.), excitation voltage: current = 40 kV: 40 mA, slit DS = 1 degree, SS open, RS open, longitudinal slit 10 mm, scanning range 2θ=5 to 65 degrees (0.02 degrees/step), and scanning speed of 1 to 10 degrees/min, the metal component contained in the hydrogenated block copolymer composition obtained in the following production examples Analyze. Thereby, the state of the titanium compound contained in the polymer was analyzed.

[(3): Determination of physical properties of adhesive composition]

(Production of adhesive composition)

100 parts by mass of the mixed hydrogenated block copolymer, 200 parts by mass of Quintone R100 (manufactured by Nippon Ryeon Co., Ltd.) as an adhesion-imparting agent, and 100 parts by mass of PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent. The mixture was heated in an oil bath while being melt-kneaded at 180 ° C for 60 minutes by a mixer (Model: L5M-A, Silverson Nippon (share), paddle type 4 leaves) to obtain a hot-melt adhesive composition. .

Further, in the adhesive composition, 1 part by mass of 2-butylbutyl-6-(3-tert-butyl acrylate as a stabilizer is formulated with respect to 100 parts by mass of the hydrogenated block copolymer composition. -2-hydroxy-5-methylbenzyl)-4-methylphenyl ester.

(Evaluation of adhesive composition)

<(3-1) Melt viscosity of adhesive composition>

The melt viscosity of the adhesive composition was measured by a Brookfield viscometer (DV-III manufactured by Brookfield Co., Ltd.) at a temperature of 180 °C. The melt viscosity was evaluated based on the obtained values by the following criteria. The order of evaluation from good is ◎, ○, △, ×.

Melt viscosity (180 ° C) (mPa ‧ s) ≦ 1500: ◎

1500 <melt viscosity (180 ° C) (mPa ‧ s) ≦ 4500: ○

4500 <melt viscosity (180 ° C) (mPa ‧ s) ≦ 8000: △

8000 <melt viscosity (180 ° C) (mPa ‧ s): ×

<(3-2) Evaluation of the cutting property of the adhesive composition>

The adhesive composition was molded into a sheet having a thickness of 1 cm, and cut into a size of 5 cm × 5 cm. Immediately after wiping the blade portion of the scissors with a gauze moistened with ethanol, the cut adhesive composition was cut with scissors. Based on the obtained results, the cutability was evaluated by the following criteria. The order of evaluation from good is ○, ×.

The adhesive composition does not remain on the scissors: ○

The case where the adhesive composition remains on the scissors: ×

(production of tape)

The molten adhesive composition was cooled to room temperature and dissolved in toluene. The obtained toluene solution was applied onto a PET film as an applicator, and thereafter, it was kept at room temperature for 30 minutes, and kept in an oven at 70 ° C for 7 minutes to completely evaporate the toluene to prepare a tape having an adhesive layer thickness of 30 μm. The obtained tape was used by the following evaluation.

(Adjustment of tape α)

<(3-3) Retention Force of Adhesive Composition>

The tape was attached to the SUS plate so as to be in contact with each other at an area of 15 mm × 25 mm, and a load of 1 kg was measured at 50 ° C until the tape was peeled off. Based on the obtained time, the retention of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ☆, ◎, ○, △, ×.

40 ≦ retention (minutes): ☆

20≦ retention (minutes) <40: ◎

5≦ Retention (minutes) <20:○

2≦ Retention (minutes) <5: △

Retention (minutes) <2: ×

<(3-4) Viscosity of adhesive composition>

The probe viscosity of the adhesive composition was determined in accordance with ASTM D2979. After attaching the tape to the weight (load 10g) at a temperature of 23 ° C, the probe (5 mm) ) The tape was brought into contact at a speed of 1 mm/sec, and after 1 second contact, the probe was peeled off at a speed of 1 mm/sec. The maximum value at this time was measured as the value of the viscosity of the probe, and the viscosity was evaluated. The order of evaluation from good is ◎, ○, △, ×.

Probe viscosity (N/5mm )≧2.0:◎

2.0>Probe viscosity (N/5mm )≧1.0:○

1.0>Probe viscosity (N/5mm )≧0.2:△

0.2> probe viscosity (N/5mm ): ×

(Adjustment of tape β)

<(3-5) Retention force of adhesive composition>

The tape was attached to the SUS plate so as to be in contact with each other at an area of 15 mm × 25 mm, and a load of 1 kg was measured at 50 ° C until the tape was peeled off. Based on the obtained time, the retention of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ○, △, ×.

150≦ retention (minutes): ○

50 ≦ retention (minutes) <150: △

Retention (minutes) <50: ×

<(3-6) Viscosity of adhesive composition>

The adhesiveness of the adhesive composition was evaluated by the inclination of the rolling ball according to JIS-Z0237. Specifically, it is prepared to have a triangular device (inclination angle of 30 degrees) in which a rigid ball, a starting path (100 mm) connecting the starting point, and an adhesive surface (100 mm) connecting the starting paths are placed on the inclined surface, and the starting point from the upper side of the inclined surface faces the lower side of the inclined surface Adhesive surface, rolling rigid ball (size: 1/32~32/32 inches). The value of 32 times the size of the ball that will stop on the adhesive surface is called the "ball number", and the maximum ball number that stops in each tape is measured. Based on the obtained ball number, the adhesiveness of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ○, △, ×.

10 ball number: ○

3 ≦ ball number <10: △

Ball number <3:×

<(3-7) Time-dependent change characteristics of the adhesive composition>

A 25 mm-wide tape was attached to a SUS plate, and a sample (K) which was allowed to stand at 23 ° C for 12 hours and a sample (L) which was allowed to stand at 60 ° C for 48 hours were prepared. The peeling speed was 300 mm/min, and the 180° peeling force at this time was measured. Based on the absolute value of the difference between the peeling force of the sample (L) and the peeling force of the sample (K), the adhesion of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ◎, ○, △, ×.

Difference in peeling force (N/10mm) <4: ◎

4≦ peeling force difference (N/10mm) <8:○

8≦ peeling force difference (N/10mm)<20:△

20≦ peeling force difference (N/10mm): ×

(Quality evaluation of tape)

<(3-8) Color tone of adhesive composition>

A 50 mm × 50 mm tape was attached to the white paper to visually evaluate the color tone of the adhesive composition through the PET film. Based on the results obtained, the color tone of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ○, △, ×.

White situation: ○

Non-white and non-yellow: △

Significant yellow situation: ×

<(3-9) Size Controllability of Adhesive Composition>

A 50 mm × 50 mm tape was attached to the white road forest paper, and it was sandwiched between two glass plates of 50 cm × 50 cm × 2 cm, and it was allowed to stand in a 60 ° C aging oven for 3 days. Based on the results obtained, the dimensional controllability of the adhesive composition was evaluated by the following criteria. The order of evaluation from good is ○, ×.

The edge of the tape is sticky: ○

The case where the edge of the tape is not sticky: ×

[(4) Preparation of hydrogenation catalyst]

In the following examples and comparative examples, a hydrogenation catalyst used in the production of a hydrogenated block copolymer was prepared by the following method. The reaction vessel equipped with the stirring device was previously replaced with nitrogen, and 1 L of the dried and purified cyclohexane was placed therein. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While thoroughly stirring the solution, a solution of 200 mmol of trimethylaluminum in n-hexane was further added, and the mixture was reacted at room temperature for about 3 days. Thereby a hydrogenation catalyst is obtained.

[(5) Preparation of hydrogenated block copolymer and hydrogenated block copolymer composition]

<Manufacturing Example 1>

An autoclave made of stainless steel having a stirrer and a sleeve of 40 L was washed, dried, and replaced with nitrogen, and charged with 5,960 g of cyclohexane, and the contents were set to 65 ° C by circulating warm water in a cannula. Add 2.0 g of N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) and n-butyl lithium cyclohexane solution (5.34 g in pure parts), and continuously add a ring containing styrene. Hexane solution (335 g in pure parts). The polymerization conversion ratio of styrene was 100%. Then, a cyclohexane solution containing 1,3-butadiene (2370 g in pure parts) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Then, a cyclohexane solution containing styrene (335 g in terms of pure fraction) was continuously added to continue the polymerization. The polymerization conversion ratio of styrene was 100%. After the second stage of polymerization of styrene, 2.21 g of methanol was added to inactivate it. The obtained solution was analyzed, and as a result, the obtained block copolymer had a styrene content of 22% by mass, and the butadiene portion had an average ethylene bond amount of 30% by mol. Further, the weight average molecular weight was 70,000.

A hydrogenation reaction is carried out by adding a hydrogenation catalyst prepared in the above manner to the block copolymer solution. The obtained hydrogenated block copolymer solution was extracted and analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond in the conjugated diene monomer unit in the obtained hydrogenated block copolymer was 75 mol%.

0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer, and sufficiently mixed. To the obtained copolymer solution, titanium oxide (manufactured by Junsei Chemical Co., Ltd.; rutile type, average particle diameter 1.5 to 2.1) is added in an amount of 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. Μm), fully mixed using Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 1.

<Manufacturing Example 2, 4>

A hydrogenated block was obtained in the same manner as in Production Example 1, except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, a coupling agent, methanol, and titanium oxide were changed to those shown in Table 1, respectively. Copolymer composition. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 1.

<Manufacturing Example 3>

A hydrogenated block copolymer solution was obtained in the same manner as in Production Example 1, except that TMEDA, n-butyllithium, styrene, 1,3-butadiene, a coupling agent, and methanol were changed to those shown in Table 1.

Water to be a hydrogenated block copolymer solution: water = 1:2 (mass ratio) was added to the hydrogenated block copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 3 containing lithium titanate as a titanium compound. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 1.

<Manufacturing Example 5, 5-H>

The autoclave made of stainless steel with a stirrer and a sleeve of 40 L was washed, dried, and replaced with nitrogen. 5960 g of cyclohexane was placed, and warm water was circulated through the casing. The material was set to 65 °C. TMEDA 1.8 g and n-butyllithium cyclohexane solution (3.85 g in pure fractions) were added, and a cyclohexane solution containing styrene (360 g in pure fractions) was continuously added. The polymerization conversion ratio of styrene was 100%. Then, a cyclohexane solution containing 1,3-butadiene (2655 g in pure fraction) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 5.70 g of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Metal Co., Ltd.) and cyclohexane were mixed at a mass ratio of 90:10. After the coupling agent was added, 0.88 g of methanol was added to inactivate it. A part of the obtained solution was subjected to analysis, and as a result, the obtained block copolymer composition had a styrene content of 12% by mass, and the butadiene portion had an average ethylene bond amount of 35 % by mol. Further, the content of the component (A) of the obtained block copolymer was 40% by mass, the weight average molecular weight was 115,000, the content of the component (B) was 60% by mass, and the weight average molecular weight was 228,000.

The hydrogenation catalyst prepared by the above method is added to the obtained hydrogenated block copolymer composition solution to carry out a hydrogenation reaction. A part of the hydrogenated block copolymer solution was extracted in the middle of the hydrogenation reaction for analysis, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 55 mol%. Water to be a hydrogenated block copolymer solution: water = 1:2 (mass ratio) was added to the hydrogenated block copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, Silica #300S-A (manufactured by Chuosilika Co., Ltd.) was mixed in a ratio of 50 ppm in terms of Si atom to the polymer solution, and suction filtration was performed using a filter having a pore diameter of 2 μm. After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 5 containing lithium titanate as a titanium compound. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 2.

Further, the hydrogenation reaction of the copolymer solution remaining after the extraction was completely carried out, and the total hydrogenation ratio was 100 mol%. 3-(3,5-) is added to 100 parts by mass of the above hydrogenated block copolymer. 0.3 parts by mass of octadecyl dibutyl-4-hydroxyphenyl)acrylate, thoroughly mixed. To the obtained copolymer solution, titanium oxide (manufactured by Junsei Chemical Co., Ltd.; rutile type, average particle diameter 1.5 to 2.1) is added in an amount of 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. Μm) Fully mixed using Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 5-H. The results of analysis of a part of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 6>

An autoclave made of stainless steel having a stirrer and a sleeve of 40 L was washed, dried, and replaced with nitrogen, and charged with 5,960 g of cyclohexane, and the contents were set to 65 ° C by circulating warm water in a cannula. TMEDA 2.5 g and n-butyllithium cyclohexane solution (5.14 g in terms of pure fraction) were added, and a cyclohexane solution containing styrene (360 g in pure fraction) was continuously added. The polymerization conversion ratio of styrene was 100%. Then, a cyclohexane solution containing 1,3-butadiene (2655 g in pure fraction) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 7.60 g of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Metal Co., Ltd.) and cyclohexane were mixed at a mass ratio of 90:10. After the coupling agent was added, 1.27 g of methanol was added to inactivate it. A part of the obtained solution was subjected to analysis, and as a result, the obtained block copolymer composition had a styrene content of 12% by mass, and the butadiene portion had an average ethylene bond amount of 35 % by mol. Further, the content of the component (A) of the obtained block copolymer was 40% by mass, the weight average molecular weight was 80,000, the content of the component (B) was 60% by mass, and the weight average molecular weight was 160,000.

The hydrogenation catalyst prepared by the above method is added to the obtained hydrogenated block copolymer composition solution to carry out a hydrogenation reaction. A part of the extraction copolymer solution was analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 55 mol%. 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer, and thoroughly mixed. Hehe. To the obtained copolymer solution, titanium oxide (manufactured by Junsei Chemical Co., Ltd.; rutile type, average particle diameter 1.5 to 2.1) is added in an amount of 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. Μm) Fully mixed using Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 6. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 7-B>

An autoclave made of stainless steel having a stirrer and a sleeve of 40 L was washed, dried, and replaced with nitrogen, and charged with 5,960 g of cyclohexane, and the contents were set to 65 ° C by circulating warm water in a cannula. TMEDA 2.6 g and n-butyllithium cyclohexane solution (5.28 g in pure parts) were added, and a cyclohexane solution containing styrene (793 g in pure fraction) was continuously added. The polymerization conversion ratio of styrene was 100%. Then, a cyclohexane solution containing 1,3-butadiene (2256 g in pure fraction) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 3.91 g of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Metal Co., Ltd.) and cyclohexane were mixed at a mass ratio of 90:10. After the coupling agent was added, 1.53 g of methanol was added to inactivate it to obtain a block copolymer solution 7. A part of the obtained solution was subjected to analysis, and as a result, the obtained block copolymer composition had a styrene content of 26% by mass, and the butadiene portion had an average ethylene bond amount of 35 % by mol. Further, the content of the component (A) of the obtained block copolymer composition was 70% by mass, the weight average molecular weight was 70,000, the content of the component (B) was 30% by mass, and the weight average molecular weight was 140,000.

To the block copolymer solution 7, 0.3 parts by mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the hydrogenated block copolymer, and thoroughly mixed. . To the copolymer solution 7, titanium oxide is added in an amount of 0.01 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom (manufactured by Pure Chemical Co., Ltd.; rutile type, average particle diameter 1.5 to 2.1) Mm) use Labolution (PRIMIX company Manufactured) thoroughly mixed. Thereafter, the solvent was removed by heating to obtain a block copolymer composition of Production Example 7-B. The results of analysis of the obtained block copolymer composition are shown in Table 2.

<Manufacturing Example 7-1>

The hydrogenation catalyst prepared in the above manner was added to the block copolymer solution 7 obtained in Production Example 7-B, and hydrogenation reaction was carried out to obtain a hydrogenated block copolymer solution 7-H. A portion of the hydrogenated block copolymer solution 7-H was subjected to analysis, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 65 mol%. Water in an amount of the hydrogenated block copolymer solution 7-H:water = 1:2 (mass ratio) was added to the copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-1 containing lithium titanate as a titanium compound. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 2.

<Manufacturing Example 7-2>

The hydrogenated block copolymer solution 7-H obtained in the production example 7-1 is added in an amount of 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom (Pure Chemical Co., Ltd. is limited) Made by the company; rutile type, average particle size 1.5 to 2.1 μm) Fully mixed using Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-2. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 7-3>

The hydrogenated block copolymer solution 7-H obtained in Production Example 7-1 was added with titanium hydride (OSAKA Titanium technologies) in terms of titanium atoms in an amount of 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer. Shares, particle size ~45 μm) were thoroughly mixed using Labolution (manufactured by PRIMIX Co., Ltd.). After heating, the solution is dissolved. The hydrogenated block copolymer composition of Production Example 7-2 was obtained. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 7-4, 7-6>

The hydrogenated block copolymer composition was obtained in the same manner as in Production Example 7-2 except that the amount of titanium oxide was changed to that shown in Table 2. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 7-5>

An equal amount of cyclohexane was added to the block copolymer solution 7 obtained in Production Example 7-B, and a hydrogenation catalyst prepared by the above method was added to carry out a hydrogenation reaction to obtain a hydrogenated block copolymer solution 7-5. Water in an amount of the hydrogenated block copolymer solution 7-5:water = 1:2 (mass ratio) was added to the copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-5 containing lithium titanate as a titanium compound. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 2.

<Manufacturing Example 7-7>

The hydrogenation catalyst prepared in the above manner was added to the block copolymer solution 7 obtained in Production Example 7-B, and hydrogenation reaction was carried out to obtain a hydrogenated block copolymer solution 7-7. A part of the hydrogenated block copolymer solution 7-7 was extracted and analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 18 mol%. Water in an amount of the hydrogenated block copolymer solution 7-7:water = 1:2 (mass ratio) was added to the copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent is removed by heating to obtain lithium titanate as a titanium compound. The hydrogenated block copolymer composition of Examples 7-7 was produced. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 2.

<Manufacturing Example 7-8>

The hydrogenated block copolymer solution 7-H obtained in the production example 7-1 is added in an amount of 0.01 part by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom (Pure Chemical Co., Ltd. is limited) The company manufactures; rutile type, average particle size 1.5 to 2.1 μm) and titanium hydride (OSAKA Titanium technologies, particle size ~150 μm) are thoroughly mixed using Labolution (manufactured by PRIMIX Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Examples 7-8. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Examples 8, 9>

The total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound was changed except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, a coupling agent, and methanol were changed as shown in Table 2, respectively. A hydrogenated block copolymer composition was obtained in the same manner as in Production Example 6, except for 40 mol%. The results of analysis of the obtained hydrogenated block copolymer composition are shown in Table 2.

<Manufacturing Example 10>

An autoclave made of stainless steel having a stirrer and a sleeve of 40 L was washed, dried, and replaced with nitrogen, and charged with 5,960 g of cyclohexane, and the contents were set to 65 ° C by circulating warm water in a cannula. TMEDA 5.5 g and n-butyllithium cyclohexane solution (10.04 g in pure parts) were added, and a cyclohexane solution containing styrene (607 g in pure fraction) was continuously added. The polymerization conversion ratio of styrene was 100%. Then, a cyclohexane solution containing 1,3-butadiene (2428 g in pure fraction) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 4.95 g of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Metal Co., Ltd.) and cyclohexane were mixed at a mass ratio of 90:10. After the coupling agent was added, 3.65 g of methanol was added to inactivate it. Extraction A part of the solution was analyzed, and as a result, the obtained block copolymer composition had a styrene content of 20% by mass, and the butadiene portion had an average ethylene bond amount of 35 % by mol. Further, the content of the component (A) of the obtained block copolymer was 80% by mass, the weight average molecular weight was 35,000, the content of the component (B) was 20% by mass, and the weight average molecular weight was 70,000.

The hydrogenation catalyst prepared by the above method is added to the obtained block copolymer composition solution to carry out a hydrogenation reaction. A part of the extracted hydrogenated block copolymer solution was analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 40 mol%.

Water to be a hydrogenated block copolymer solution: water = 1:2 (mass ratio) was added to the hydrogenated block copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). The mixture was allowed to stand for separation and the copolymer solution was separated. Thereafter, the hydrogenated block copolymer solution was separated by a centrifugal separator (manufactured by Kubota Trading Co., Ltd.), and only the supernatant of the copolymer solution was taken. 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer composition, and the mixture was sufficiently mixed. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 10. The results of analysis of a part of the obtained hydrogenated block copolymer are shown in Table 2.

<Manufacturing Example 11>

The polymerization was carried out by the following method using a tank reactor having an internal volume of 10 L and a stirring device and a jacket. After cyclohexane was charged into the reactor and adjusted to a temperature of 70 ° C, n-butyllithium and TMEDA were added, and then a cyclohexane solution containing 14 parts by mass of styrene as a monomer was added. The polymerization conversion ratio of styrene was 100%.

Next, a cyclohexane solution containing 75 parts by mass of butadiene and a cyclohexane solution containing 11 parts by mass of styrene were continuously supplied to the reactor at a constant rate. At this time, the addition speed is adjusted and added so that the addition of the two solutions starts to be the same as the end of the addition. The polymerization conversion ratio of styrene and butadiene was 100%.

Next, a solution of Epotohto ZX-1059 in cyclohexane was added, and methanol was added to inactivate it. A part of the obtained solution was subjected to analysis, and as a result, the total content of styrene in the obtained block copolymer composition was 25% by mass, and the content of styrene which was 25 or more was 14% by mass, and the component (A) and the component (B). Each has a random block represented by Ar-D/Ar and (Ar-D/Ar) 2X, and the average ethylene bond amount of the butadiene portion is 40 mol%. Further, the content of the component (A) of the obtained block copolymer was 70% by mass, the weight average molecular weight was 90,000, the content of the component (B) was 30% by mass, and the weight average molecular weight was 180,000.

The hydrogenation catalyst prepared by the above method is added to the obtained block copolymer composition solution to carry out a hydrogenation reaction. A part of the extracted hydrogenated block copolymer solution was analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 50 mol%.

Water having a mass ratio of the obtained hydrogenated block copolymer solution to water of 1:2 was added to the copolymer solution, and mixed with Labolution (manufactured by PRIMIX Co., Ltd.). After standing and separating the copolymer solution, 0.3 mass of 3-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acrylate was added to 100 parts by mass of the above hydrogenated block copolymer. Mix well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 11 containing lithium titanate as a titanium compound. The amount of titanium per 100 parts by mass of the hydrogenated block copolymer was 0.009 parts by mass, and the amount of titanium having a particle diameter of 0.1 to 100 μm was 98 vol%.

<Example 1>

Using the hydrogenated block copolymer composition of Production Example 1, a hot-melt adhesive composition was obtained by the method for producing the above-mentioned adhesive composition. Further, an adhesive tape is obtained by the above-described method for producing a tape. The physical properties of the adhesive composition (the evaluation of the adhesive composition, the evaluation of the adhesive tape, and the quality evaluation of the adhesive tape) were carried out using the adhesive composition and the tape. These results are shown in Table 3.

<Examples 2 to 7, 9 to 12, 15 to 19>

The hydrogenated block copolymer composition of the production examples 2 to 6, 7-1, 7-2, 7-3, 7-5, 7-6, 7-7, 7-8, 8, 9, 11 was used instead. In addition to the hydrogenated block copolymer of Production Example 1, The same procedure as in Example 1 was carried out, and an adhesive composition and a tape were separately prepared to evaluate characteristics. These results are shown in Table 3.

<Example 8>

In place of the hydrogenated block copolymer composition of Production Example 7 except that the hydrogenated block copolymer composition of Production Example 7 was used, Arkon M100 (manufactured by Arakawa Chemical Industries Co., Ltd.) was used instead of Quintone R100 (Japan Ryeon Co., Ltd.) The adhesive composition and the tape were prepared in the same manner as in Example 1 except for the production, and the properties were evaluated. These results are shown in Table 3.

<Examples 13 to 14>

In place of the hydrogenated block copolymer composition of Production Example 5, 7-1, the hydrogenated block copolymer composition of Production Example 1 was used, and I-Marv S100 (manufactured by Idemitsu Kosan Co., Ltd.) was used instead of Quintone R100 (Japan Rui In the same manner as in Example 1, except for the production of Weng (share), an adhesive composition and a tape were prepared, and the properties were evaluated. These results are shown in Table 3.

<Examples 20 to 22, Comparative Example 1>

The same procedure as in Example 1 was carried out except that the hydrogenated block copolymer composition of Production Example 5-H, Production Example 7-B, Production Example 10, and Production Example 7-4 was used instead of the hydrogenated block copolymer composition of Production Example 1. In the same operation, an adhesive composition and a tape were separately prepared to evaluate characteristics. These results are shown in Table 3.

<Examples 23 to 36>

(A1) non-hydrogenated styrene-isoprene block copolymer

(A1-1) D1161 (manufactured by Kraton Polymers)

SI/SIS, styrene content 16% by mass, SI content 20% by mass

(A1-2) Quintac 3520 (made by Japan's Swiss company)

SI/SIS, styrene content 15% by mass, SI content 78% by mass

(A2) hydrogenated styrene-butadiene block copolymer

(A2-1) G1726 (manufactured by Kraton Polymers)

SEB/SEBS, styrene content 30% by mass, SEB content 70% by mass

(A2-2) G1652 (manufactured by Kraton Polymers)

SEBS, styrene content 30% by mass, SEB content 0%

(A2-3) G1657 (manufactured by Kraton Polymers)

SEB/SEBS, styrene content 13% by mass, SEB content 30%

(A3) hydrogenated styrene-isoprene block copolymer

(A3-1) Septon 2063 (manufactured by Kuraray Co., Ltd.)

(A3-2) Septon 2043 (manufactured by Kuraray Co., Ltd.)

(A3-3) Septon 2007 (manufactured by Kuraray)

(A3-4) Septon 2277 (manufactured by Kuraray Co., Ltd.)

(A3-5) Septon 4033 (manufactured by Kuraray Co., Ltd.)

(B) Adhesive agent

(B1) Quintone R100 (aliphatic petroleum hydrocarbon resin / manufactured by Japan Rayon Co., Ltd.)

(B2) Clearon P125 (hydrogenated terpene resin / manufactured by Yasuhara Chemical Co., Ltd.)

(C) softener

(C1) Diana Process Oil NS90S (made of naphthenic oil / Idemitsu Kosan Co., Ltd.)

(D) Antioxidants

(D1) Irganox 1010 (manufactured by Ciba Specialty Chemicals)

A hot-melt adhesive composition was obtained by the above-described method of producing the adhesive composition, in addition to the components shown in Table 4, and the tape was obtained by the above-described method for producing a tape. The physical properties of the adhesive composition (the evaluation of the adhesive composition, the evaluation of the adhesive tape, and the quality evaluation of the adhesive tape) were carried out using the adhesive composition and the tape. These results are shown in Table 4.

The tape obtained in Examples 33 and 34 was cut into 50 mm × 50 mm, attached to a SUS plate, and the SUS plate was placed on the side facing the south with the adhesive layer irradiated to the sunlight. Set. After two weeks, the release tape felt an odor due to deterioration of the adhesive layer. At this time, the scent of the tape of Example 34 was weaker than that of the tape of Example 33.

[Industrial availability]

The adhesive composition of the invention can be used for various adhesive tapes, adhesive sheets, adhesive films, adhesive labels, pressure sensitive sheets, pressure sensitive sheets, surface protection sheets, surface protection films, sanitary Materials, various light plastic molded products for fixing pastes, carpet fixing pastes, tile fixing pastes, adhesives, etc., especially for adhesive tapes, It is industrially usable for adhesive sheets, adhesive films, adhesive labels, surface protective sheets, surface protective films, and adhesives for sanitary materials.

Claims (13)

A hydrogenated block copolymer composition comprising: a hydrogenated block copolymer having a polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit and a polymer block mainly composed of a conjugated diene monomer unit In the titanium compound, the content of the titanium compound is 0.000001 to 2 parts by mass based on 100 parts by mass of the hydrogenated block copolymer. The hydrogenated block copolymer composition according to claim 1, wherein the total hydrogenation ratio of the unsaturated double bond in the conjugated diene monomer unit is 5 mol% or more and less than 90 mol%. The hydrogenated block copolymer composition of claim 1 or 2, wherein the conjugated diene monomer unit contains a butadiene monomer unit. The hydrogenated block copolymer composition according to any one of claims 1 to 3, wherein the polymer block mainly comprising the vinyl aromatic hydrocarbon monomer unit has an average molecular weight of more than 7,500 and 150,000 or less. The hydrogenated block copolymer composition according to any one of claims 1 to 4, wherein the content of the titanium compound is 0.000001 to 0.05 parts by mass based on 100 parts by mass of the hydrogenated block copolymer, in terms of titanium atom. The hydrogenated block copolymer composition according to any one of claims 1 to 5, wherein the content of the titanium compound is more than 0.0075 parts by mass and less than 0.02 parts by mass based on 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom. . The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the titanium compound contains at least one selected from the group consisting of titanium oxide, lithium titanate, hydrous titanium oxide, and titanium hydroxide. The hydrogenated block copolymer composition according to any one of claims 1 to 7, wherein 80 vol% or more of the titanium compound is a particle having a particle diameter of 0.1 to 100 μm. The hydrogenated block copolymer composition according to any one of claims 1 to 8, which comprises a hydrogenated block copolymer (A) and a hydrogenated block copolymer (B) as the above hydrogenated block copolymer, and the above hydrogenated block The copolymer (A) has the above polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit and the above polymer block mainly composed of a conjugated diene monomer unit, and the hydrogenated block copolymer (B) And having at least two polymer blocks mainly composed of a vinyl aromatic hydrocarbon monomer unit and the above polymer block mainly composed of a conjugated diene monomer unit, wherein the hydrogenated block copolymer (B) is opposite The ratio of the weight average molecular weight of the hydrogenated block copolymer (A) (the weight average molecular weight of the hydrogenated block copolymer (B)) / (the weight average molecular weight of the hydrogenated block copolymer (A)) is 1.3~ 10, the content of the hydrogenated block copolymer (A) is 20% by mass or more and 90% by mass or less based on 100% by mass of the total of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). The content of the above hydrogenated block copolymer (B) relative to the above hydrogenated block copolymer (A) and the above The total block copolymer (B) is 100% by mass of 10 mass%, 80 mass% or less. An adhesive composition comprising 100 parts by mass of the hydrogenated block copolymer composition according to any one of claims 1 to 9 and 20 to 700 parts by mass of the adhesion-imparting agent. The adhesive composition of claim 10, which contains an aromatic vinyl-based elastomer. The adhesive composition of claim 10 or 11, which comprises a conjugated diene-based synthetic rubber. The adhesive composition according to any one of claims 10 to 12, which contains natural rubber.