JP2016089171A - Hydrogenated block copolymer composition and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenated block copolymer composition becoming adhesive composition excellent in color tone, dimensional control property and die cut property and good balance thereof and an adhesive composition using the same.SOLUTION: There is provided a hydrogenated block copolymer composition containing a hydrogenated block copolymer having a polymer block mainly containing a vinyl aromatic hydrocarbon monomer unit and a polymer block mainly containing a conjugated diene monomer unit and a titanium compound with the content of the titanium compound of 0.000001 to 2 pts.mass based on 100 pts.mass of the hydrogenated block copolymer in terms of titanium atom.SELECTED DRAWING: None

Description

  The present 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, environmental impact reduction, etc., and vinyl aromatic carbonization as a base polymer for hot-melt adhesives. A hydrogen monomer-conjugated diene monomer block copolymer (for example, SBS: styrene-butadiene-styrene-block copolymer) is widely used.

  For example, Patent Document 1 discloses an adhesive composition composed of a triblock copolymer and a diblock copolymer. Patent Document 2 discloses an adhesive composition composed of 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 obtained by hydrogenating a block copolymer of a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer at a specific ratio. Yes.

JP 61-278578 A JP-A 63-248817 JP 05-98130 A

  However, even with the above-described conventionally proposed techniques, the effect of improving the color tone, dimensional controllability, and die cutability is still insufficient, and the balance between these is still insufficient.

  The present invention has been made in view of the above-described problems of the prior art, and is excellent in color tone, dimensional controllability, and die-cutting properties, and is a hydrogenated block that becomes an adhesive composition excellent in these balances. It aims at providing a copolymer composition and an adhesive composition using the same.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have obtained a hydrogenated block copolymer composition having a specific structure, and its hydrogenated block copolymer composition and tackifier It was found that the adhesive composition containing a predetermined amount of each of the above can solve the above-mentioned problems of the prior art, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, and a hydrogenated block copolymer having a polymer block mainly composed of conjugated diene monomer units;
A titanium compound,
The content of the titanium compound is 0.000001 to 2 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms.
Hydrogenated block copolymer composition.
[2]
The total hydrogenation rate of unsaturated double bonds in the conjugated diene monomer unit is 5 mol% or more and less than 90 mol%,
[1] The hydrogenated block copolymer composition according to [1].
[3]
The hydrogenated block copolymer composition according to [1] or [2], wherein the conjugated diene monomer unit includes a butadiene monomer unit.
[4]
The average molecular weight of the polymer block mainly composed of the vinyl aromatic hydrocarbon monomer unit is more than 7,500 and not more than 150,000, according to any one of [1] to [3]. Hydrogenated block copolymer composition.
[5]
The content of the titanium compound is 0.000001 to 0.05 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms, according to any one of [1] to [4]. A hydrogenated block copolymer composition.
[6]
Any of [1] to [5], wherein the content of the titanium compound is more than 0.0075 parts by mass and 0.02 parts by mass or less with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The hydrogenated block copolymer composition according to claim 1.
[7]
The hydrogenation block according to any one of [1] to [6], wherein the titanium compound includes at least one selected from the group consisting of titanium oxide, lithium titanate, hydrous titanium oxide, and titanium hydroxide. Copolymer composition.
[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 includes a hydrogenated block copolymer (A) and a hydrogenated block copolymer (B),
The hydrogenated block copolymer (A) has a polymer block mainly composed of the vinyl aromatic hydrocarbon monomer unit and a polymer block mainly composed of the conjugated diene monomer unit. ,
The hydrogenated block copolymer (B) has at least two polymer blocks mainly composed of the vinyl aromatic hydrocarbon monomer unit, and a polymer block mainly composed of the conjugated diene monomer unit; Have
Ratio of weight average molecular weight of the hydrogenated block copolymer (B) to the hydrogenated block copolymer (A) (weight average molecular weight of the hydrogenated block copolymer (B)) / (the hydrogenated block copolymer) The weight average molecular weight of the polymer (A) is 1.3 to 10,
The content of the hydrogenated block copolymer (A) is 20% by mass or more and 90% by mass with respect to 100% by mass in total of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). Mass% or less,
The content of the hydrogenated block copolymer (B) is 10% by mass to 80% with respect to a total of 100% by mass of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). Mass% or less,
The hydrogenated block copolymer composition according to any one of [1] to [8].
[10]
[100] 100 parts by mass of the hydrogenated block copolymer composition according to any one of [1] to [9];
20 to 700 parts by weight of a tackifier,
Containing an adhesive composition.
[11]
Containing an aromatic vinyl elastomer,
[10] The adhesive composition according to [10].
[12]
Containing a conjugated diene-based synthetic rubber,
[10] or the adhesive composition according to [11].
[13]
Contains natural rubber,
[10] to [12] The adhesive composition according to any one of [12].

  According to the present invention, a hydrogenated block copolymer composition that is an adhesive composition excellent in color tone, dimension controllability, and die-cutting properties, and in an excellent balance thereof, and an adhesive composition using the same Can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

  In the following, the structural unit constituting the polymer is referred to as “˜monomer unit”, and when described as a polymer material, “unit” is omitted, and simply “˜monomer” is described. To do.

[Hydrogenated block copolymer composition]
The hydrogenated block copolymer composition of the present embodiment contains a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units and a polymer block mainly composed of conjugated diene monomer units. A hydrogenated block copolymer and a titanium compound are contained, and the content of the titanium compound is 0.000001 to 2 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms.

[Hydrogenated block copolymer]
The hydrogenated block copolymer of this embodiment is a polymer block (Ar) mainly composed of at least one vinyl aromatic hydrocarbon monomer unit and a polymer mainly composed of at least one conjugated diene monomer unit. Block (D).

  The weight average molecular weight of the hydrogenated block copolymer is preferably 2,000 or more, more preferably 10,000 or more, and further 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, and further 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. Moreover, when the weight average molecular weight of the hydrogenated block copolymer is 1,000,000 or less, a hydrogenated block copolymer and an adhesive composition having excellent low melt viscosity characteristics and productivity can be obtained. It tends to be. The weight average molecular weight of the hydrogenated block copolymer can be determined by the method described in the examples.

  In the present specification, “mainly composed of vinyl aromatic hydrocarbon monomer units” means that the content of vinyl aromatic hydrocarbon monomer units in the polymer block is 60% by mass or more, preferably It means 80% by mass or more, more preferably 95% by mass or more. When the content of the vinyl aromatic hydrocarbon monomer unit in the polymer block is 60% by mass or more, a hydrogenated block copolymer composition and an adhesive composition having excellent holding power can be obtained. .

  Further, in the present specification, “mainly comprising a conjugated diene monomer unit” means that the content of the conjugated diene monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass or more. More preferably, it means 90% by mass or more, and more preferably 95% by mass or more.

Although it does not specifically limit as a structure of a hydrogenated block copolymer, For example, following formula (i)-(vi) is mentioned.
(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 vinyl aromatic hydrocarbon monomer units, and D represents a polymer block mainly composed of conjugated diene monomer units. (D) represents, X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium, m, n and k represent an integer of 1 or more, It is preferably an integer. When there are a plurality of polymer blocks (Ar) and / or polymer blocks (D), the weight average molecular weight, composition and structure of each polymer block (Ar) and / or each polymer block (D) May be the same or different, but when a plurality of polymer blocks (Ar) are present, a plurality of polymer blocks (Ar) are present from the viewpoint of holding power, heat resistance, and productivity. ) Is preferably as small as possible. Further, the value obtained by dividing the content of vinyl aromatic hydrocarbon monomer units contained in each polymer block (Ar) by the number of polymer blocks (Ar), and the vinyl aromatic occupying in the hydrogenated block copolymer. It is preferable that the difference in the value obtained by dividing the content of the group hydrocarbon monomer unit by the number of polymer blocks (Ar) is smaller.

  The difference in the weight average molecular weight of the plural polymer blocks (Ar) is not particularly limited, but the weight average molecular weight of the other polymer block (Ar) with respect to the polymer block (Ar) having the largest weight average molecular weight. The difference is preferably 35% or less of the weight average molecular weight of the polymer block (Ar) having the largest weight average molecular weight, more preferably 25% or less, further preferably 15% or less, and even more preferably 5% or less. preferable. Moreover, although there is no restriction | limiting in particular, It is preferable that it is 0% or more.

  In addition, the weight average molecular weight of a polymer block (Ar) can be calculated | required by the measuring method as described in an Example.

  The value obtained by dividing the content of vinyl aromatic hydrocarbon monomer units contained in each polymer block (Ar) by the number of polymer blocks (Ar) and the vinyl aromatic carbonization in the hydrogenated block copolymer The difference in the value obtained by dividing the content of hydrogen monomer units by the number of polymer blocks (Ar) is not particularly limited, but the content of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer is not limited. It is preferably 7% or less of the value obtained by dividing the amount by the number of polymer blocks (Ar), more preferably 5% or less, still more preferably 3% or less, and even more preferably 1% or less. Moreover, although there is no restriction | limiting in particular, It is preferable that it is 0% or more.

  In addition, the vinyl aromatic compound monomer unit content contained in each polymer block (Ar) is extracted in small amounts at the end of polymerization of the polymer block (Ar) and the polymer block (D), and is described in the examples. By measuring the content of the vinyl aromatic hydrocarbon monomer unit by the above method and calculating 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 further preferably 10% by mass. % Or more. 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, and still more preferably 80% by mass or less. It is. The hydrogenated block copolymer and the adhesive composition having excellent adhesive performance and excellent balance due to the content of the vinyl aromatic hydrocarbon monomer unit being in the above range. Tends to be obtained. In particular, when the content of the vinyl aromatic hydrocarbon monomer unit is 5% by mass or more, a hydrogenated block copolymer having excellent holding power tends to be obtained. 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 tack and productivity can be obtained. is there. When used for applications such as an adhesive tape, it is preferably 10% by mass or more, more preferably 12% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less. When used for applications such as pressure-sensitive adhesive labels, 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, more preferably 30% by mass or less. When used for applications such as hygiene, it is preferably at least 12% by mass, more preferably at least 25% by mass, even more preferably at least 30% by mass, preferably at most 70% by mass, more preferably at most 68% by mass. The hydrogenated block copolymer and the adhesive composition having excellent adhesive performance and excellent balance due to the content of the vinyl aromatic hydrocarbon monomer unit being in the above range. Tends to be obtained. In addition, content of the vinyl aromatic hydrocarbon monomer unit in a hydrogenated block copolymer can be measured by the method described in the Example mentioned later.

  Further, the vinyl 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 vinyl bond amount of the conjugated diene monomer unit before hydrogenation is preferably 15 mol% or more, more preferably 18 mol% or more, and further preferably 20 mol% or more. More specifically, the vinyl bond amount 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. More preferably, it is 20 mol% or more and 85 mol% or less. When the vinyl bond amount of the conjugated diene monomer unit is within the above range, excellent properties in productivity and adhesive properties tend to be obtained.

  Here, the amount of vinyl bonds refers to the total amount of conjugated diene monomer units incorporated in the 1,2-bond, 3,4-bond, and 1,4-bond bond modes before hydrogenation. , The ratio of the total mol amount of conjugated diene monomer units incorporated by 1,2-bond and 3,4-bond. After hydrogenation, 1,2-bond without hydrogen addition, 1,2-bond after hydrogen addition, 3,4-bond without hydrogen addition, 3,4-bond after hydrogen addition, no hydrogen addition 1,4-bond and 1,2-bond after hydrogenation, and 1,2-bond after hydrogenation, with respect to the total molar amount of conjugated diene monomer units incorporated in the form of 1,4-bond after hydrogenation. The ratio of the total molar amount of conjugated diene monomer units incorporated by 1,2-bond, 3,4-bond without hydrogen addition and 3,4-bond after hydrogenation is the conjugated diene before hydrogenation. Equal to the vinyl bond amount of the monomer unit. Therefore, the amount of vinyl bonds in the conjugated diene monomer unit before hydrogenation can be measured by nuclear magnetic resonance spectrum analysis (NMR) using the block copolymer after hydrogenation. It can be measured by the method described.

  The content of the vinyl aromatic hydrocarbon monomer unit and the value of the weight average molecular weight are almost the same before and after hydrogenation, so the value after hydrogenation is adopted.

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

  In the hydrogenation step, the conjugated bond of the vinyl aromatic hydrocarbon monomer unit may be hydrogenated, but from the viewpoint of holding power and adhesive strength, the hydrogen of the conjugated bond of the all vinyl aromatic hydrocarbon monomer unit. The addition rate is preferably 30 mol% or less, preferably 10 mol% or less, and more preferably 3 mol% or less.

  In addition, the total hydrogenation rate of unsaturated double bonds 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 power and tack. Preferably it is 15 mol% or more, More preferably, it is 20 mol% or more. The total hydrogenation rate of unsaturated double bonds in the conjugated diene monomer unit in the hydrogenated block copolymer is preferably less than 90 mol%, more preferably 88 mol% or less, from the viewpoint of low melt viscosity. More preferably, it is 87 mol% or less. When the hydrogenation rate is 5 mol% or more, a hydrogenated block copolymer having excellent holding power and tack tends to be obtained. In addition, when the hydrogenation rate is less than 90 mol%, a hydrogenated block copolymer and an adhesive composition having excellent tack and low melt viscosity characteristics tend to be obtained. In addition, the hydrogenation rate of the conjugated diene monomer unit in the hydrogenated block copolymer can be measured by the method described in Examples.

  In the polymer block (Ar) of the present embodiment, the content of the vinyl aromatic hydrocarbon monomer unit that is 25 mer or more is preferably 90% by mass or more, and more preferably 93% by mass or more. 95 mass% or more is more preferable, and 98 mass% or more is further more preferable. Moreover, although it does not specifically limit, 100 mass% or less is preferable. In the polymer block (Ar), the content of the vinyl aromatic hydrocarbon monomer unit that is 25 mer or more is in the above range, so that the adhesive block has excellent adhesive performance and the balance thereof. Also, an excellent hydrogenated block copolymer and an adhesive composition tend to be obtained. In particular, when the content is 90% by mass or more, a hydrogenated block copolymer having excellent holding power and heat resistance tends to be obtained. Moreover, it exists in the tendency for the hydrogenated block copolymer and adhesive composition which have the outstanding productivity to be obtained by being 100 mass% or less. In addition, the content of the vinyl aromatic hydrocarbon monomer unit which is 25 mer or more is the content of the polymer block component composed of the vinyl aromatic hydrocarbon monomer unit determined by the measurement method described in the Examples. It can be determined using the weight (however, the vinyl aromatic polymer component having an average degree of polymerization of 24 or less is excluded).

  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, and further preferably Is 10,000 or more, and even more preferably 11,500 or more. 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, and even more preferably 20,000 or less. It is. When the average molecular weight of the polymer block (Ar) exceeds 7,500, a hydrogenated block copolymer having excellent holding power tends to be obtained. Further, when the average molecular weight of the polymer block (Ar) is 150,000 or less, a hydrogenated block copolymer and an adhesive composition having excellent tack tend to be obtained. 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, the polymer block ( When Ar) is 2 or more, it means the average molecular weight of those blocks. The average molecular weight of the polymer block (Ar) can be controlled within the above range by adjusting various conditions of the production method described later. Moreover, the average molecular weight of a polymer block (Ar) can be measured by the method as described in an Example.

  As the hydrogenated block copolymer of the present embodiment, the following hydrogenated block copolymer (A) (hereinafter also referred to as “component (A)”) from the viewpoint of improving the balance between the adhesive property and the low melt viscosity property. And a hydrogenated block copolymer (B) (hereinafter, also referred to as “component (B)”) may have a hydrogenated block copolymer having two different structures. Here, the component (A) is a hydrogenated block polymer containing at least one polymer block (Ar) and at least one polymer block (D), and the component (B) is at least two polymers. It is a hydrogenated block polymer containing a block (Ar) and 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 with respect to the total amount of the component (A) and the component (B) of 100% by mass. It is below, More preferably, it is 30 to 80 mass%, More preferably, it is 40 to 75 mass%.

  The content of the component (B) is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass with respect to the total amount of the component (A) and the component (B) of 100% by mass. Or less, more preferably 20% by mass or more and 70% by mass or less, and still more preferably 25% by mass or more and 60% by mass or less.

  Due to the content of component (A) and component (B) being within the above range, both the low melt viscosity property and the adhesive property are excellent, and the hydrogenated block copolymer composition and adhesive are well balanced. There is a tendency to obtain an adhesive composition. In addition, content of a component (A) and a component (B) can be controlled within the said range by adjusting various conditions of the manufacturing method mentioned later. Moreover, content of a component (A) and a component (B) can be measured by the method described in the Example mentioned later. In addition, although the value of content of a component (A) and a component (B) becomes substantially the same value before and after hydrogenation, the value after hydrogenation is employ | adopted.

  The ratio of the weight average molecular weight of component (B) to the weight average molecular weight of component (A) in the case of including component (A) and component (B) [(weight average molecular weight of component (B)) / (component (A) Weight average molecular weight)] is 1.3 or more and 10 or less, preferably 1.5 or more and 8.0 or less, and more preferably 1.8 or more and 5.0 or less. The ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) is within the above range, so that the hydrogenated block coexisting with excellent low melt viscosity property and adhesive property, and with excellent balance. There exists a tendency for a polymer composition and an adhesive composition to be obtained.

  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 controlled within the above range by adjusting various conditions of the production method described later. Moreover, ratio of content of a component (A) and a component (B), a weight average molecular weight, and a weight average molecular weight can be measured by the method described in the Example mentioned later.

  When the component (A) or component (B) is included as the hydrogenated block copolymer, the content of the vinyl aromatic hydrocarbon monomer unit is not a value for each component, but the entire hydrogenated block copolymer Content, that is, the average value of the content of each component.

  When the component (A) and the component (B) are included as the hydrogenated block copolymer, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is not the value for each component, but the hydrogenated block copolymer. It is an average value of the vinyl bond amount as a whole polymer, that is, the vinyl bond amount of each component.

  Also, the total hydrogenation rate of unsaturated double bonds in the conjugated diene monomer unit in the hydrogenated block copolymer is not a value for each component, but the vinyl bond amount as a whole of the hydrogenated block copolymer, that is, It is an average value of the vinyl bond amount of each component.

Hereinafter, each component will be described in more detail.
(Ingredient (A))
Component (A) includes a polymer block (Ar) mainly composed of at least one vinyl aromatic hydrocarbon monomer unit and a polymer block (D) mainly composed of at least one conjugated diene monomer unit, It is preferable to contain.

  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, and further preferably 20,000 or more. Further, the weight average molecular weight of the hydrogenated block copolymer of component (A) is preferably 500,000 or less, more preferably 200,000 or less, and further preferably 150,000 or less. When the weight average molecular weight of component (A) is 2,000 or more, it has excellent holding power and productivity, and when the weight average molecular weight of component (A) is 500,000 or less, it has excellent low melting. A hydrogenated block copolymer composition and an adhesive composition having viscosity characteristics are obtained. In addition, the weight average molecular weight of a component (A) can be calculated | required by the method described in an Example.

Although it does not specifically limit as a structure of a component (A), For example, following formula (i)-(vi) is mentioned.
(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), D represents a polymer block (D), X represents a residue of a coupling agent or polyfunctional organic lithium, etc. Represents a residue of a polymerization initiator, m, n and k each represent an integer of 1 or more, each preferably an integer of 1 to 6, and Ar in the case where a plurality thereof is present, is a vinyl aromatic hydrocarbon monomer The types of D may be the same or different, and when there are a plurality of D, the types and molecular weights of the conjugated diene monomers may be the same or different, but when there are a plurality of Ar The above-described embodiment is preferably used.)

  Among the formulas (i) to (vi), a hydrogenated block copolymer containing one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit is preferable. Ar-D, D A hydrogenated block copolymer represented by -Ar-D is more preferred. When component (A) has such a structure, a hydrogenated block copolymer composition and an adhesive composition having excellent low melt viscosity characteristics, adhesive strength, and excellent balance are obtained. It tends to be.

(Ingredient (B))
Component (B) includes a polymer block (Ar) mainly composed of at least two vinyl aromatic hydrocarbon monomer units and a polymer block (D) mainly composed of at least one conjugated diene monomer unit, It is preferable to contain.

  The weight average molecular weight of the hydrogenated block copolymer of component (B) is preferably 4,000 or more, more preferably 10,000 or more, and further preferably 20,000 or more. Moreover, the weight average molecular weight of the hydrogenated block copolymer of a component (B) becomes like this. Preferably it is 1,000,000 or less, More preferably, it is 400,000 or less, More preferably, it is 300,000 or less. When the weight average molecular weight of the component (B) is 4,000 or more, the holding power and productivity tend to be further improved. In addition, when the weight average molecular weight of component (B) is 1,000,000 or less, a hydrogenated block copolymer composition and an adhesive composition having excellent low melt viscosity characteristics tend to be obtained. is there. In addition, the weight average molecular weight of a component (B) can be calculated | required by the method described in an Example.

Further, the structure of the component (B) is not particularly limited, but for example, the following formula (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 vinyl aromatic hydrocarbon monomer units, and D represents a polymer mainly composed of conjugated diene monomer units. Represents a block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organolithium, e and f represent an integer of 2 or more, g represents an integer of 1 or more, Each of them is preferably a positive integer of 6 or less, and Ar in the case of plural occurrences may be the same or different types of vinyl aromatic hydrocarbon monomers. The type and molecular weight of the monomer may be the same or different, but when a plurality of Ar are present, the above-described embodiment is preferably used.

Among the formulas (vii) to (xiii), the formulas (vii), (ix), (xi), (x
ii) A hydrogenated block copolymer represented by (e = 2, g = 1, f = 2-4) is preferred. When the component (B) has such a structure, the balance of the adhesiveness performance and the productivity tend to be further improved.

[Method for producing hydrogenated block copolymer]
A hydrogenated block copolymer is a polymerization step in which a polymer is obtained by polymerizing at least a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent using an organolithium compound as a polymerization initiator. A hydrogenation step of hydrogenating a double bond in a conjugated diene monomer unit of a polymer and a desolvation step of desolvating a solvent of a solution containing a hydrogenated block copolymer are sequentially produced. be able to. The weight average molecular weight of the hydrogenated block copolymer can be adjusted, for example, by controlling the type and addition amount of a coupling agent described later. Also, the weight average molecular weight can be adjusted by controlling the addition amount and the number of additions of the polymerization initiator, which will be described later, and adding them in multiple portions.

  When two hydrogenated block copolymers having two different structures of component (A) and component (B) are included as the hydrogenated block copolymer, component (A) and component (B) are produced separately. Then, they may be mixed later or manufactured simultaneously. When the component (A) and the component (B) are produced simultaneously, the weight average molecular weight, the ratio of the weight average molecular weight and the content of the component (A) and the component (B) are, for example, the types and addition amounts of coupling agents described later Can be adjusted by controlling. Moreover, the weight average molecular weight of a component (A) and a component (B), ratio of a weight average molecular weight, and content also contain by controlling the addition amount and addition frequency of a polymerization initiator which are mentioned later, and adding in multiple times. The amount can be adjusted. In addition, by controlling the addition amount of the deactivator described later, once performing the deactivation step, and further continuing the polymerization reaction, the weight average molecular weight of the component (A) and the component (B), the ratio of the weight average molecular weight and The content can be adjusted.

(Polymerization process)
The polymerization step is a step of obtaining a polymer by polymerizing a monomer containing at least a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent using an organolithium compound as a polymerization initiator.

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

<Hydrocarbon solvent>
As described above, a hydrocarbon solvent is used in the polymerization step. Although it does not specifically limit as hydrocarbon solvent, For example, Aliphatic hydrocarbons, such as butane, pentane, hexane, isopentane, heptane, octane; Cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. alicyclic Hydrocarbons: aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and the like. A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

<Polymerization initiator>
In the polymerization step, at least an organolithium compound is used as a polymerization initiator. The organic lithium compound is not particularly limited, and examples thereof include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound in which one or more lithium atoms are bonded in the molecule. More specifically, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium and the like can be mentioned. It is done. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  The polymerization initiator may be added to the reaction solution in a plurality of times. By carrying out like this, the composition containing the multiple types of block copolymer from which a weight average molecular weight and a structure differ can be obtained at once.

<Monomer used for polymerization>
The conjugated diene monomer constituting the polymer block (D) is a diolefin having a pair of conjugated double bonds. The conjugated diene monomer is not particularly limited. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3- Examples include pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are preferable. Moreover, 1,3-butadiene is more preferable from the viewpoint of improving the holding power of the adhesive composition. A conjugated diene monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl aromatic hydrocarbon monomer constituting the polymer block (Ar) is not particularly limited. For example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N , N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and the like. Of these, styrene is preferable from the viewpoint of economy. A vinyl aromatic hydrocarbon monomer may be used individually by 1 type, and may use 2 or more types together.

  The block copolymer may contain a monomer unit other than the vinyl aromatic hydrocarbon monomer unit and the conjugated diene monomer unit. In the polymerization step, the vinyl aromatic hydrocarbon monomer and the conjugated diene unit are included. In addition to the monomer, other monomers copolymerizable with the monomer can be used.

<Polar compound and randomizing agent>
In the polymerization process, adjustment of the polymerization rate, control of the microstructure (cis, trans, vinyl ratio) of the polymerized conjugated diene monomer unit, reaction between the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer A predetermined polar compound or a randomizing agent can be used for the purpose of adjusting the ratio.

  Although it does not specifically limit as a polar compound or a randomizing agent, For example, Ethers, such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether; Amines, such as a triethylamine and tetramethylethylenediamine; Examples thereof include acid salts, alkoxides of potassium and sodium.

<Coupling agent>
In the polymerization step, a solution containing a vinyl aromatic-conjugated diene block copolymer having an active end is added in an amount such that the functional group is less than 1 mol equivalent with respect to the active end, and the formulas (iv) to (vi) ), (X) to (xiii), a coupling agent represented by X may be added.

  The coupling agent to be added is not particularly limited, but any bifunctional or higher functional coupling agent can be used. Although it does not specifically limit as a bifunctional coupling agent, For example, Bifunctional halogenated silanes, such as dichlorosilane, monomethyldichlorosilane, dimethyldichlorosilane; Diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldi Bifunctional alkoxysilanes such as ethoxysilane; Bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, dibromomethane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyl Bifunctional tin halides such as dichlorotin and dibutyldichlorotin; dibromobenzene, benzoic acid, CO, 2-chloropropene and the like.

  The trifunctional coupling agent is not particularly limited, and examples thereof include trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; methyltrimethoxysilane; And trifunctional alkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane.

  The tetrafunctional coupling agent is not particularly limited, and examples thereof include tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane. Tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; tetrafunctional tin halides such as tetrachlorotin and tetrabromotin;

  The pentafunctional or higher functional coupling agent is not particularly limited, and examples thereof include 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, decabromodiphenyl ether, and the like. . In addition, polyvinyl compounds such as epoxidized soybean oil, 2 to 6 functional epoxy group-containing compounds, carboxylic acid esters, and divinylbenzene can also be used. A coupling agent may be used individually by 1 type, and can also be used in combination of 2 or more type.

  Among these, a non-halogen coupling agent is preferable from the viewpoint of color tone and low adverse effect on the plant. From the viewpoint of productivity and low adverse effect on the plant, an epoxy group-containing compound and an alkoxysilane are preferable.

  As described above, when a coupling agent is added to a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end in an amount such that the functional group is less than 1 mol equivalent to the active end, In some block copolymers among the aromatic vinyl-conjugated diene block copolymers having ends, active ends are bonded to each other through a residue of a coupling agent. Then, the remaining part of the vinyl aromatic-conjugated diene block copolymer having an active terminal remains in the solution unreacted. In the reaction using these coupling agents, the coupling rate can be controlled by adjusting the type and amount of the coupling agent.

  The polymerization method carried out in the polymerization step in the polymer production method of the present embodiment is not particularly limited, and known methods can be applied. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43- 17979, JP-B 46-32415, JP-B 49-36957, JP-B 48-2423, JP-B 48-4106, JP-B 56-28925, JP-A 59-166518 And the methods described in JP-A-60-186577 and the like.

<Deactivator>
In the polymerization step, a quencher may be added. Although it does not specifically limit as a deactivator, Water or alcohol etc. are known. Among these, alcohol is preferable from the viewpoint of deactivation efficiency. The quenching agent may be added at any timing in the polymerization process. If the deactivator to be added is less than 100 mol% of the active terminal, the conjugated diene monomer and / or the vinyl aromatic hydrocarbon monomer may be further added after the deactivator is added. In this way, the polymerization reaction between the active terminal that has not been deactivated and the conjugated diene monomer and / or vinyl aromatic hydrocarbon monomer continues, and a polymer solution containing polymers of different molecular weights can be obtained. it can.

  Further, when two hydrogenated block copolymers having different structures of the component (A) and the component (B) are included, the content of the component (A) and the component (B) in the deactivation step is It can control by adjusting the addition molar amount of the quencher with respect to the addition amount. As the added molar amount of the deactivator increases, the content of the component (A) increases, and as the added molar amount of the deactivator decreases, the content of the component (B) tends to decrease.

  Further, after adding the deactivator, a conjugated diene monomer and / or a vinyl aromatic hydrocarbon monomer is added, and the polymerization reaction is continued, whereby the weight average molecular weight and the weight average of the component (A) and the component (B). The molecular weight ratio can be controlled. Specifically, as the amount of the conjugated diene monomer and / or vinyl aromatic hydrocarbon monomer added after the deactivator is added, the weight average molecular weight of the component (B) increases, and the weight increases accordingly. The ratio of average molecular weight also tends to increase.

(Hydrogenation process)
The hydrogenation step is a step of converting a double bond in at least the conjugated diene monomer of the polymer obtained in the polymerization step into a hydrogenated product by a hydrogenation reaction. Specifically, a hydrogenated block copolymer solution can be obtained by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent. At that time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount and the like.

  The catalyst used in the hydrogenation reaction is not particularly limited. For example, (1) a supported type in which a metal such as Ni, Pt, Pd, or Ru is supported on a support such as carbon, silica, alumina, or diatomaceous earth. So-called Ziegler type catalysts using homogeneous catalysts and (2) organic salts such as Ni, Co, Fe, Cr or acetylacetone salts and reducing agents such as organic Al, or so-called organics such as organometallic compounds such as Ru and Rh A homogeneous catalyst using a complex catalyst or a titanocene compound using organic Li, organic Al, organic Mg or the like as a reducing agent is known. Among these, a homogeneous catalyst system using organic Li, organic Al, organic Mg, or the like as a reducing agent for the titanocene compound is preferable from the viewpoint of economy, colorability of the polymer, or adhesive strength.

  The hydrogenation reaction temperature is preferably 0 to 200 ° C, more preferably 30 to 150 ° C. Moreover, the pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and further preferably 0.3 to 5 MPa. Furthermore, the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction may be a batch process, a continuous process, or a combination thereof.

  The hydrogenation method is not particularly limited. For example, the methods described in JP-B-42-8704, JP-B-43-6636, JP-B-63-4841 and JP-B-63-5401 are described. Is mentioned.

  The hydrogenation reaction is not particularly limited, but it is preferably performed after the step of deactivating the active terminal of the polymer described later from the viewpoint of high hydrogenation activity.

(Desolvation process)
The solvent removal step is a step of removing the hydrocarbon solvent of the solution containing the polymer. The solvent removal method is not particularly limited, and examples thereof include a method of removing the solvent by a steam stripping method or a direct solvent removal method.

  The amount of residual solvent in the polymer obtained by the polymer production method is preferably 2% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less. And even more preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less.

  Moreover, it is preferable to add antioxidant from the viewpoint of the heat aging resistance of the block copolymer of this embodiment, or suppression of gelatinization. The antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant as a radical scavenger, a phosphorus-based antioxidant as a peroxide decomposer, and a sulfur-based antioxidant. Moreover, you may use the antioxidant which has both performances together. These may be used alone or in combination of two or more. Among these, it is preferable to add at least a phenolic antioxidant from the viewpoint of heat aging resistance of the polymer and suppression of gelation.

  In addition, from the standpoint of preventing coloration of the polymer and high mechanical strength, a decalcification step for removing metals in the polymer and a neutralization step for adjusting the pH of the polymer, for example, addition of acid or addition of carbon dioxide gas May be.

  The hydrogenated block copolymer of the present embodiment that can be produced as described above has a polar group-containing functional group containing an atom selected from the group consisting of nitrogen, oxygen, silicon, phosphorus, sulfur, and tin in the block copolymer. A so-called modified polymer bonded or a modified block copolymer obtained by modifying a block copolymer component with a modifying agent such as maleic anhydride may also be included. Such a modified copolymer can be obtained by performing a known modification reaction on the hydrogenated block copolymer obtained by the above-described method.

  A method for imparting these functional groups is not particularly limited. For example, a method of adding a functional group to a polymer using a compound having a functional group as an initiator, a monomer, a coupling agent, or a stopper. Is mentioned.

  Although it does not specifically limit as an initiator containing a functional group, For example, the initiator containing N group is preferable, Dioctylamino lithium, di-2-ethylhexyl amino lithium, ethyl benzylamino lithium, (3- (dibutylamino) -Propyl) lithium, piperidino lithium and the like.

  The monomer containing a functional group is not particularly limited. For example, the monomer used for the above-described polymerization may be a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, or an alkoxysilane. And compounds containing groups. Among these, a monomer containing an N group is preferable, and N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzylamine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene N, N-dimethyl-2- (4-vinylbenzyloxy) ethylamine, 4- (2-pyrrolidinoethyl) styrene, 4- (2-piperidinoethyl) styrene, 4- (2-hexamethyleneiminoethyl) styrene, 4- (2-morpholinoethyl) styrene, 4- (2-thiazinoethyl) ) Styrene, 4- (2-N-methyl-piperazino-ethyl) styrene, 1 - ((4-vinyl) methyl) pyrrolidine, 1- (4-vinyl benzyloxycarbonyl) pyrrolidine, and the like.

  Furthermore, the coupling agent and the terminating agent containing a functional group are not particularly limited. For example, among the coupling agents described above, a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, an alkoxy group. Examples thereof include compounds containing a silane group. Among these, a coupling agent containing an N group or an O group is preferable. Tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline Γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxy Examples thereof include propyldiethylethoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone and the like.

[Titanium compound]
The hydrogenated block copolymer composition of this embodiment contains a titanium compound. Content of a titanium compound is 0.000001-2 mass parts with respect to 100 mass parts of hydrogenation block copolymers in conversion of a titanium atom. Here, “in terms of titanium atom” means the amount of titanium atoms in a titanium compound including 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. For example, crystalline titanium oxide such as rutile type, anatase type and brookite type; hydrous titanium oxide such as amorphous titanium oxide, orthotitanic acid and metatitanic acid; Examples thereof include composite oxides of titanium and different metals such as titanium, lithium titanate, barium titanate, and strontium titanate. Among these, it is preferable that the titanium compound includes at least one selected from the group consisting of titanium oxide, hydrous titanium oxide, titanium hydroxide, and lithium titanate. By using such a titanium compound, the color tone tends to be more excellent. These may be used alone or in combination of two or more.

  Further, the titanium compound may include a reaction product of a titanium compound used as a hydrogenation catalyst for the conjugated diene polymer. By using such a titanium compound, it tends to be more excellent in economy and productivity. Specifically, when the block copolymer is a hydrogenated block copolymer hydrogenated using a titanium compound, the hydrogenated block copolymer may contain a titanium compound. Therefore, for example, this titanium compound may be prepared to be a titanium compound having a particle size of 0.1 to 100 μm, and the content of the titanium compound may be controlled to be 0.000001 to 2 parts by mass. Specifically, for example, a titanium compound as a catalyst is converted into titanium oxide by contact with water or the like, and the obtained titanium oxide particles are grown to a predetermined particle diameter. When the titanium compound is grown by contact with water, the particle tends to grow as the contact time and frequency increase, depending on the content of the titanium compound and the amount of water. The content of the titanium compound can be controlled by a method such as filtration.

  The content of the titanium compound having a particle size of 0.1 μm or more and 100 μm or less is preferably 80 vol% or more, more preferably 85 vol% or more, further preferably 90 vol%, with respect to the total amount of titanium compound of 100 vol%. That's it. The upper limit of the content of the titanium compound having a particle size 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, a hydrogenated block copolymer composition and an adhesive composition that are excellent in adhesive properties, dimensional controllability, and die-cutting properties tend to be obtained. In addition, when the hydrogenated block copolymer 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 above-mentioned “particle diameter is 0.1 μm or more and 100 μm or less. “Content of titanium compound” can be read as “content of metal compound having a particle size of 0.1 μm to 100 μm”.

  More preferably, the content of the titanium compound having a particle size of 0.1 μm or more and 50 μm or less is 80 vol% or more and 100 vol% or less with respect to the total amount of titanium compound of 100 vol%, and more preferably the particle size is The content of the titanium compound of 0.1 μm or more and 30 μm or less is 80 vol% or more and 100 vol% or less with respect to the total amount of titanium compound of 100 vol%. By having such a particle size distribution, a hydrogenated block copolymer composition and an adhesive composition that are excellent in dimensional controllability and die-cutting properties tend to be obtained. When the hydrogenated block copolymer 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 above-mentioned “particle diameter is 0.1 μm or more and 50 μm or less. The “content of the titanium compound” can be read as “the content of the metal compound having a particle size of 0.1 μm to 50 μm”.

  Content of a titanium compound is 0.000001 mass part with respect to 100 mass parts of hydrogenation block copolymers in conversion of a titanium atom, Preferably it is 0.00001 mass part or more, More preferably, it is 0.0001 mass. Part or more, more preferably 0.0005 part by weight or more, and even more preferably exceeding 0.0075 part by weight. Further, the content of the titanium compound is 2 parts by mass or less with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atom, and is preferably 1 part by mass or less from the viewpoint of holding power and tack, preferably 0. 0.05 parts by mass or less, more preferably 0.025 parts by mass or less, and still more preferably 0.02 parts by mass or less. When the content of the titanium compound is 0.000001 parts by mass or more, it has excellent color tone, dimensional controllability, and die-cutting properties, and when it is 2 parts by mass or less, it has excellent productivity and economically. There is a tendency to obtain advantageous hydrogenated block copolymer compositions and adhesive compositions. Moreover, when content of a titanium compound is more than 2 mass parts, there exists a tendency for the retention strength and tack | tuck of an adhesive composition to be impaired.

  The average particle size of the titanium compound is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, and still more preferably 0.1 to 20 μm. By such an average particle diameter, it is possible to obtain excellent color tone, dimensional controllability, die-cutting properties, and a good balance between these and adhesive properties.

  Content of a titanium compound can be calculated | required by the method as described in the below-mentioned Example. The average particle size of the titanium compound contained in the conjugated diene polymer is measured by analyzing a polymer solution obtained by dissolving the titanium-containing composition in an inert solvent using a laser diffraction particle size distribution analyzer. it can. More specifically, it can be determined by the method described in the examples.

  When the titanium-containing composition contains metal compound particles other than the titanium compound, for example, when the metal compound contains a titanium compound and a lithium compound, the “particle diameter of the titanium compound” is “the particle diameter of the metal compound” Can be read as Here, the “particle diameter of the metal compound” means the particle diameter of particles composed of a titanium compound and another metal compound, or the particle diameter of titanium compound particles and other metal compound particles.

  The method for producing a hydrogenated block copolymer containing a titanium compound or a hydrogenated block copolymer composition containing a titanium compound is not particularly limited, and a solid conjugated diene polymer and a titanium compound are plastomil. , A method of dispersing in a hydrogenated block copolymer or a hydrogenated block copolymer composition by mixing using an extruder, a roll, etc., a hydrogenated block copolymer or a hydrogenated block copolymer composition After adding the titanium compound to the polymer solution in which the solution is dissolved and stirring the solution, the solvent is removed by heating or depressurizing operation, titanium alkoxide and water are added to the polymer solution to hydrolyze the titanium alkoxide, Examples thereof include a method of generating a titanium compound in the system. At this time, the particle diameter can be controlled by controlling the mixing method (stirring method). In addition, as described above, a hydrogenated block copolymer or a hydrogenated block copolymer containing a titanium compound so that a titanium compound having a particle size of 0.1 to 100 μm is formed in the hydrogenated block copolymer composition, or A hydrogenated block copolymer composition containing a titanium compound may be prepared.

[Adhesive composition]
The adhesive composition of the present embodiment includes 100 parts by mass of the above-described hydrogenated block copolymer or hydrogenated block copolymer composition, 20 to 700 parts by mass of a tackifier to be described later, and as necessary. It is preferable to contain the other component mentioned later. Such an adhesive composition of this embodiment has an excellent holding power, tack, low melt viscosity characteristics, color tone, dimensional controllability, and die-cutting properties, and an excellent balance of these. It becomes.

  In addition, the adhesive composition of this embodiment is a polymer other than component (A) and component (B) (for example, polyolefin; polyolefin copolymer; styrene-butadiene block copolymer, styrene-isoprene). Block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene block copolymer Aromatic vinyl-based elastomers such as coalescence; other rubbers) may be contained. In this case, with respect to a total content of 100 parts by mass of these polymers and the component (A) and the component (B) of this embodiment, a tackifier described later: 20 to 500 parts by mass, and a softener described later : 0 to 300 parts by mass are included.

  In addition, according to a use, the weight average molecular weight of the component (A) and (B) in a hydrogenated block copolymer composition is selected, and the compounding quantity of each component, such as a tackifier and a softener, is adjusted. It is preferable.

(Tackifier)
A wide variety of tackifiers can be selected depending on the intended use and required performance of the resulting adhesive composition. Examples of the tackifier include, but are not limited to, natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin, hydrogen Rosin compounds such as pentaerythritol ester of added rosin; natural terpene copolymer, three-dimensional polymer of natural terpene, aromatic modified terpene resin, hydrogenated derivative of aromatic modified terpene resin, terpene phenol resin, hydrogenation of terpene phenol resin Terpene compounds such as derivatives, terpene resins (monoterpenes, diterpenes, triterpenes, polypertenes, etc.), hydrogenated terpene resins, etc .; aliphatic petroleum hydrocarbon resins (C5 resins), aliphatic petroleum hydrocarbon trees Hydrogenated derivatives of the above, aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated derivatives of aromatic petroleum hydrocarbon resins, dicyclopentadiene resins, hydrogenated derivatives of dicyclopentadiene resins, C5 / C9 copolymer systems Examples thereof include petroleum hydrocarbon compounds such as resins, hydrogenated derivatives of C5 / C9 copolymer resins, cycloaliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins. These tackifiers can be used alone or in combination of two or more.

  As the tackifier, a liquid type tackifying resin having a color tone of colorless to light yellow and substantially free from odor and having good thermal stability can be used.

  Hereinafter, the preferable tackifier according to a use and performance is demonstrated more concretely.

(Tackifier for hydrogenated derivatives)
From the viewpoint of difficulty in coloring and low odor, the tackifying resin is preferably a hydrogenated derivative. The hydrogenated derivative is not particularly limited. For example, a hydrogenated derivative of rosin resin, a hydrogenated derivative of rosin ester, a hydrogenated derivative of aromatic modified terpene resin, a hydrogenated derivative of terpene phenol resin; an aliphatic petroleum hydrocarbon Hydrogenated derivatives of resins (C5 resins), hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated derivatives of dicyclopentadiene resins, hydrogenated derivatives of modified dicyclopentadiene resins, C5 / Examples thereof include hydrogenated derivatives of C9 copolymer resins and hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins. Of these, hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated derivatives of dicyclopentadiene resins, and the like are particularly preferable. Although it does not specifically limit as a commercial item of such a hydrogenation derivative, Alcon P90, Alcon P100, Alcon P115, Alcon P125 (Arcon P140 (brand name)) made by Arakawa Chemical Co., Ltd. Alcon M90, Alcon M100, Alcon M115, Alcon M135 (trade name), Ester Gum H, Ester Gum HP (trade name), High Pale (trade name), Ligalite R1010, Ligalite R1100, Ligalite R5100, Ligalite S5100, Ligalite R7100, Ligalite C6100 (product) Name), East Tuck C100W, East Tuck C100L, East Tuck C100R, East Tuck C115W, East Tuck C115R (Product Name), Stepelite E (Product Name), Foral A E (trade name), Stepelite Ester 10E (trade name), Clearon P (trade name), Clearon M (trade name), Clearon K (trade name), YS Polystar UH (trade name), Exxon, manufactured by Yashara Chemical Co., Ltd. Escollets 5340, Escorets 5320, Escorets 5300, Escorets 5380, Escorets 5400, Escorets 227E, Escorets 5600, Escorets 5690 (trade name), Quinton A100, Quinton B170, Quinton M100, Quinton R100, Quinton S195, Quinton D100, Quinton U185, Quinton DX395, Quinton 390N, Quinton N180, Quinton G100B, Quinton G115, Quinton E200SN, Qui Ton D200, Quinton 1105, Quinton 1325, Quinton 1340 (trade name) Imabu S100, Imabu S110, Imabu P100, Imabu P125, Imabu P140 (trade name) manufactured by Idemitsu Kosan Co., Ltd. ) And the like.

(Tackifiers other than hydrogenated derivatives)
The tackifier other than the hydrogenated derivative is not particularly limited. For example, natural rosin, polymerized rosin, modified rosin, natural rosin glycerol ester, modified rosin glycerol ester, natural rosin pentaerythritol ester, modified rosin penta Rosin ester such as erythritol ester; natural terpene copolymer, natural terpene three-dimensional polymer, aromatic modified terpene resin, terpene phenol resin, terpene resin; pinene resin, aliphatic petroleum hydrocarbon resin (C5 resin), Aromatic petroleum hydrocarbon resins (C9 resins), dicyclopentadiene resins, C5 / C9 copolymer resins, and cyclic aliphatic petroleum hydrocarbon resins. Among these, aliphatic petroleum hydrocarbon resins (C5 series), aromatic petroleum hydrocarbon resins (C9 series resins), C5 / C9 copolymer resins, cyclic aliphatic petroleum hydrocarbon resins, terpene resins, natural and modified rosins. Esters, as well as mixtures thereof, are preferred. As a commercial item, Arakawa Chemical Co., Ltd. ester gum AA-L, ester gum A, ester gum AAV, ester gum, ester gum 105, ester gum AT, Bencel A, Bencel AZ, Bencel C, Bencel D125, Bencel D160 (product) Name), Superester (trade name), Tamanoru (trade name), Pine Crystal (trade name), Aradim (trade name), Wingtack 10, Wingtack 95, Wingtack 98, WingtackExtra, Wingtack RWT-7850, Wingtack PLUS, WingtackPLET, Wingtack PLUS, Wingtack PLUS, Wingtack Wingtack 86 (trade name), Norsolene (product name), Piccotac 8095 manufactured by Eastman Chemical Co., Pi cotac 1095, Piccotac 1098, Piccotac 1100 (trade name), Escollets 1102, Escorets 1202, Escorets 1204LS, Escorets 1304, Escorets 1310, Escorets 1315, Escorets 224, Escorets 2101, Escorets 213, Escorets 213, Escolets 807, manufactured by ExxonMobil Chemical Sylvagum (trade name) and Sylvalite (trade name) manufactured by Arizona Chemical Co., Ltd., Piccolite (trade name) manufactured by Ashland, YS resin PX (trade name), YS resin PXN (trade name), YS polystar manufactured by Yasuhara Chemical Co., Ltd. U (product name), YS polystar T (product name), YS polystar S (product name), YS polystar G (product name) YS Polystar N (Product Name), YS Polystar K (Product Name), YS Polystar TH (Product Name), YS Resin TO (Product Name), YS Resin TR (Product Name), YS Resin SX (Product Name), Maruzen Petroleum Examples include Marcaretz M (trade name) manufactured by Kagakusha.

(Aliphatic tackifier)
From the viewpoint of obtaining an adhesive composition having high tackiness and high holding power, and from the viewpoint of economy, it is preferable to use an aliphatic tackifier as the tackifier. Examples of the aliphatic tackifier include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins (C5 resins), and C5 / C9 copolymer systems. And hydrogenated derivatives of C5 / C9 copolymer resins, cycloaliphatic petroleum hydrocarbon resins, and cycloaliphatic petroleum hydrocarbon resins. The aliphatic tackifier has an aliphatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. More preferably, it refers to a tackifier that is 88% by mass or more, and more preferably 95% by mass or more. When the content of the aliphatic hydrocarbon group is within the above range, the tackiness, holding power and economy tend to be further improved.

  The aliphatic tackifier can be produced by homopolymerizing 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 or cyclohexyl group. Further, other monomers that can be used in the copolymerization are not particularly limited. For example, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3- Examples include butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpenes, and terpene-phenol resins.

(Aromatic tackifier)
From the viewpoint of obtaining an adhesive composition having high adhesive strength, high cohesive strength, and high coatability, or improving the balance between cohesive strength and tack of the adhesive composition, It is preferable to use a group-based tackifier. The aromatic tackifier is not particularly limited, and examples thereof include aromatic petroleum hydrocarbon resins (C9 resins) and C5 / C9 copolymer resins. The aromatic tackifier has an aromatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. More preferably, the tackifier is 88% by mass or more, and more preferably 95% by mass or more. When the content of the aromatic hydrocarbon group is within the above range, the adhesive force and the coating property tend to be further improved.

  The aromatic tackifier can be produced by homopolymerizing 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. For example, styrene, α-methylstyrene, vinyltoluene, methoxystyrene, TERT-butylstyrene, chlorostyrene, indene monomer (methylindene) Are included). Further, other monomers that can be used in the copolymerization are not particularly limited. For example, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3- Examples include butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpenes, and terpene-phenol resins. Commercially available products include Endex 155 (trade name), Crystallex 1120, Crystallex 3085, Crystallex 3100, Crystallex 5140, Crystallex F100 (tradename), Plastrin 240, Plastrin, manufactured by Eastman Chemical Co., Ltd. 290, Picotex 100 (trade name), Knit Resin Coumarone G-90, V-120, V-120S (trade name) manufactured by Nikkiso Chemical.

(Tackifier having affinity for block copolymer glass phase (eg, polymer block (Ar)) and / or non-glass phase (eg, polymer block (D)) block
As an adhesive composition, one having high adhesiveness, one having a low change in adhesive strength and creep performance (smaller value is better), one having low melt viscosity, one having high heat resistance, and those From the viewpoint of obtaining a good balance, it has an affinity for the non-glass phase block (for example, polymer block (D), usually an intermediate block) of the block copolymer contained in the adhesive composition. 20 to 75% by mass of a certain tackifier, and 0.1 to 30 tackifier having an affinity for a block of a glass phase of a block copolymer (for example, a polymer block (Ar), usually an outer block). It is more preferable to contain by mass. Here, the block copolymer is a concept including components (A) and (B).

  The tackifier having affinity for the non-glass phase block of the block copolymer (for example, the polymer block (D)) is not particularly limited, but examples thereof include rosin compounds, terpene compounds, aliphatic petroleum carbonization. Hydrogenated resin (C5 resin), hydrogenated derivative of aliphatic petroleum hydrocarbon resin, C5 / C9 copolymerized resin, hydrogenated derivative of C5 / C9 copolymerized resin, cyclic aliphatic petroleum hydrocarbon resin, cycloaliphatic And hydrogenated derivatives of petroleum hydrocarbon resins.

  The content of the tackifier having affinity for the non-glass phase of the block copolymer is preferably 20 to 75% by mass, more preferably 25 to 70% with respect to 100% by mass of the adhesive composition. It is mass%, More preferably, it is 30-65 mass%.

  Although it does not specifically limit as a tackifier which has affinity for the block (for example, polymer block (Ar)) of the glass phase of a block copolymer, For example, resin which has an aromatic ring in a molecule | numerator is preferable. Such a resin is not particularly limited, and examples thereof include aromatic group-containing resins such as a homopolymer or a copolymer containing vinyltoluene, styrene, α-methylstyrene, coumarone, or indene as a structural unit. It is done. Further, among these, crystallex, plastrin, picotex (trade name, manufactured by Eastman Chemical Co.) having α-methylstyrene is preferable.

  The content of the tackifier having affinity for the block of the glass phase of the block copolymer is preferably 0.5 to 30% by mass, more preferably 100% by mass with respect to the adhesive composition 100% by mass. It is 1-20 mass%, More preferably, it is 2-12 mass%.

  From the viewpoint of obtaining an adhesive composition having high initial adhesive strength, high wettability, low melt viscosity or high coatability, a petroleum resin having an aroma content of 3 to 12% by mass as a tackifier Is preferably used. Such a petroleum resin is not particularly limited. For example, an aliphatic petroleum hydrocarbon resin (C5 resin), a hydrogenated derivative of an aliphatic petroleum hydrocarbon resin (C5 resin), an aromatic petroleum hydrocarbon resin ( C9 resin), hydrogenated derivatives of aromatic petroleum hydrocarbon resins (C9 resins), dicyclopentadiene resins, hydrogenated derivatives of dicyclopentadiene resins, C5 / C9 copolymer resins, C5 / C9 copolymers And hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins, and cyclic aliphatic petroleum hydrocarbon resins. The aroma content of the petroleum resin is preferably 3 to 12% by mass, more preferably 4 to 10% by mass. Of these, hydrogenated petroleum resin is particularly preferable.

  From the viewpoint of obtaining an adhesive composition having high initial adhesive strength, high wettability, low melt viscosity, high coating property, and the like, it is preferable to use a styrene oligomer as a tackifier. The styrene oligomer is not particularly limited, and examples thereof include aromatic petroleum hydrocarbon resins (C9-based resins) such as Piccolastic A5 (trade name) and Piccolastic A75 (trade name, manufactured by Eastman Chemical Co.).

  The content of the styrene oligomer is preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less with respect to 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, etc., as a tackifier, a hydrogenated resin (for example, the above hydrogenated resin) Derivatives) are preferably used.

  The content of the tackifier is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, with respect to 100 parts by mass of the hydrogenated block copolymer composition. Preferably it is 75 mass parts or more. Moreover, content of a tackifier is 700 mass parts or less with respect to 100 mass parts of block copolymer compositions, Preferably it is 500 mass parts or less, More preferably, it is 400 mass parts or less, 350 It is below mass parts. Moreover, content of a tackifier is 20-700 mass parts with respect to 100 mass parts of block copolymer compositions, Preferably it is 20-500 mass parts, More preferably, it is 30-400 mass parts. Yes, more preferably 50 to 350 parts by mass, even more preferably 75 to 350 parts by mass. When the content of the tackifier is within the above range, the adhesive property is further improved.

  In addition, when the adhesive composition of this embodiment contains polymers other than the component (A) and component (B) which are mentioned later, content of a tackifier is contained in an adhesive composition. It is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 75 parts by mass or more with respect to 100 parts by mass in total of the polymer. Moreover, content of a tackifier is 500 mass parts or less with respect to a total of 100 mass parts of the polymer contained in an adhesive composition, Preferably it is 400 mass parts or less, 350 mass parts or less. It is. When the content of the tackifier is within the above range, the adhesive property is further improved. Here, the polymer contained in the adhesive composition refers to component (A), component (B) and aromatic vinyl-based elastomer, conjugated diene-based synthetic rubber, and natural rubber described later.

(Softener)
“Softening agent” refers to an agent that functions to lower the hardness of the adhesive composition and lower the viscosity. Although it does not specifically limit as a softening agent, For example, petroleum-type oils, such as well-known paraffin type process oil, naphthenic process oil, aroma type process oil, extender oil, and these mixed oils; Vegetable oil; Plasticizer Synthetic liquid oligomers; and mixtures thereof.

  Hereinafter, the preferable softener according to a use and performance is demonstrated more concretely.

  Oils can be used from the viewpoint of viscosity reduction, tackiness improvement, and low hardness of the adhesive composition. Although it does not specifically limit as oils, For example, well-known paraffin type process oil, naphthenic process oil, aroma type process oil, extender oil, and these mixed oil etc. are mentioned. Paraffinic process oils are preferred from the viewpoint of low temperature characteristics, aging resistance, stain resistance, and color tone, and aroma based process oils are preferred from the viewpoint of compatibility. Low temperature characteristics, aging resistance, stain resistance, color tone, compatibility A naphthenic process oil is preferable from the viewpoint of balance.

  When using an adhesive composition as a transdermally absorbable preparation, a plasticizer is used as a softener from the viewpoint of improving transdermal absorbability and storage stability and improving drug solubility in the adhesive composition. can do. Although it does not specifically limit as a plasticizer, For example, Liquid paraffin; Fatty acid which consists of C12-C16 higher fatty acid and C1-C4 lower monohydric alcohols, such as isopropyl myristate, ethyl laurate, and isopropyl palmitate Esters; fatty acids having 8 to 10 carbon atoms; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol; oils and fats such as olive oil, castor oil, squalene, and lanolin; ethyl acetate, ethyl alcohol Dimethyl decyl sulfoxide, decyl methyl sulfoxide, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, dimethyl lauryl amide, dodecyl pyrrolidone, isosorbitol, olefin Organic solvents such as alcohol and lauric acid; liquid surfactants; ethoxylated stearyl alcohol, glycerin ester, isotridecyl myristate, N-methylpyrrolidone, ethyl oleate, oleic acid, diisopropyl adipate, octyl palmitate, 1, Examples include 3-propanediol and glycerin. Among these, a liquid compound is used at room temperature. Among these, glycerin ester is preferable, and medium-chain fatty acid triglyceride which is an ester of 8 to 10 fatty acids and glycerin is more preferable. Examples of the medium chain fatty acid triglyceride include tri (caprylic acid / capric acid) glyceryl. A plasticizer may be used individually by 1 type, or may use 2 or more types together.

  When using an adhesive composition and an adhesive tape as medical adhesive tapes, such as a taping tape, it is preferable to use it combining liquid paraffin and another plasticizer.

  When using an adhesive composition and an adhesive tape for a medical use, the addition amount of a plasticizer is preferably 3 to 30 mass%, more preferably 100 mass% with respect to the adhesive composition. It is 3-20 mass%, More preferably, it is 3-10 mass%. When the addition amount of the liquid plasticizer is 3% by mass or more, transdermal absorbability, storage stability, and drug solubility in the adhesive composition tend to be further improved. Moreover, it exists in the tendency for the cohesion force of an adhesive composition to improve more because the addition amount of a liquid plasticizer is 20 mass% or less.

  In order to make the adhesive composition softer, a synthetic liquid oligomer can be used from the viewpoint of improving the bleeding property. The synthetic liquid oligomer may be referred to as a liquid rubber and is not particularly limited, and examples thereof include a styrene oligomer, a butadiene oligomer, an isoprene oligomer, a butene oligomer, and an isobutylene oligomer.

When it is desired to use a naturally-derived component as a softener, vegetable oil is used. Although it does not specifically limit as vegetable oil, A castor oil, tall oil, a pine tar etc. are mentioned. Castor oil is preferred from the viewpoint of cold resistance.
Although it does not specifically limit as a plasticizer, Dibasic acid ester, such as DBP and DOP, etc. are mentioned.

  Although it does not specifically limit as a commercial item of such a softener, For example, Idemitsu Kosan Co., Ltd. Diana Fresia S32, 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 Bloom 350 (trade name) manufactured by Kukdong Oil & Chem, DN Oil KP-68 (trade name), Enperper M1930 (trade name) manufactured by BP Chemicals, Kaydol (trade name) manufactured by Crompton, Primol 352 manufactured by Esso Product name), PetroChina Company KN4010 (trade name) manufactured by Kobe Oil Chemical Co., Ltd., SYNTAC N-40, N-60, N-70, N-75, N-80, SYNTAC PA-95, PA-100, PA-140, SYNTAC HA-10 , HA-15, HA-30, HA-35 (product name), JOMO process P200, P300, P500, 750, JOMO process R25, R50, R200, R1000, JOMO process X50, X100E, X140 (product) manufactured by Japan Energy Name), Nippon San Oil Co., Ltd., Samper 110, 115, 120, 130, 150, 2100, 2280, Sansen Oil 310, 410, 415, 420, 430, 450, 380, 480, 3125, 4130, 4240, JSO Aroma 790 , Nitoprene 720L (trade name), Fujikop Co., Ltd. Processes P-100, P-200, P-300, P-400, P-500, Fukkor Newflex 1060W, 1060E, 1150W, 1150E, 1400W, 1400E, 2040E, 2050N, Fukkor Aromax 1, 3, 5 , EXP1 (trade name), Shelf Rex 371JY (trade name) manufactured by Shell Japan, Petrex Process Oil PN-3, PN-3M, PN-3N-H (trade name), Petlex Examples thereof include process oils LPO-R, LPO-V, PF-2 (trade name), and Cosmo Process 40, 40A, 40C, 200A, 100, 1000 (trade name) manufactured by Cosmo Oil Lubricants.

  Moreover, content of a softening agent is 0-300 mass parts with respect to 100 mass parts of block copolymer compositions, Preferably it is 10-175 mass parts, More preferably, it is 20-150 mass parts. . When the content of the softening agent is within the above range, the adhesive property is further improved.

  Moreover, it is preferable that it is 35 mass% or less with respect to an adhesive composition, and, as for content of a softening agent, it is more preferable that it is 3 mass% or more and 30 mass% or less. When the content of the softening agent is within the above range, the adhesive property is further improved.

  In addition, when the adhesive composition of this embodiment contains polymers other than the component (A) and component (B) which are mentioned later, content of a softening agent is contained in an adhesive composition. It is 0-300 mass parts with respect to a total of 100 mass parts of a polymer, Preferably it is 10-175 mass parts, More preferably, it is 20-150 mass parts. When the content of the softening agent is within the above range, the adhesive property is further improved.

(Other ingredients)
The adhesive composition of this 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 necessary. .

(Polymer other than component (A) and component (B))
Although it does not specifically limit as polymers other than a component (A) and a component (B), For example, polyolefin, polyolefin-type copolymer, aromatic vinyl-type elastomer, and other rubber | gum are mentioned. In the present specification, “other than the component (A) and the component (B)” means not corresponding to any of the component (A) and the component (B).

  Although there is no limitation in content of polymers other than a component (A) and a component (B), the sum total of a component (A) and a component (B) is a component (A), a component (B), and a component (A ) And the polymer other than the component (B) is preferably 10 parts by mass or more with respect to 100 parts by mass in total. The total of component (A) and 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. There may be 80 mass parts or more, and 90 mass parts or more may be sufficient. Moreover, it is not necessary to contain polymers other than a component (A) and a component (B).

  The polyolefin and polyolefin-based copolymer may be crystalline or non-crystalline, and may coexist, and is not particularly limited. For example, ethylene, propylene, 1-butene, 1-pentene, 1- Examples thereof include polymers composed of one or more monomers such as hexene, 4-methyl-1-pentene, 1-octene and 1-decene, atactic polypropylene, and ethylene-ethyl acrylate copolymer. As a commercially available polyolefin, VESTOPLAST 308, VESTOPLAST 408, VESTOPLAST 508, VESTOPLAST 520, VESTOPLAST 608, VESTOPLAST 703, VESTOPLAST 704, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 708, VESTOPLAST 891, VESTOPLAST EPNC702, VESTOPLAST EP807, VESTOPLAST 206, VESTOPLAST EP2403, VESTOPLAST 2412, (product name), Lic made by Clariant Japan cene PP1302, Licocene PP1502, Licocene PP1602, Licocene PP2602 (trade name), and the like.

  Although it does not specifically limit as an aromatic vinyl type elastomer, For example, a styrene-ethylene type block copolymer, a styrene-butadiene type block copolymer, a styrene-propylene type block copolymer, a styrene-isoprene type block copolymer Styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene-isoprene block copolymer, etc. And polymers other than the component (A) and the component (B).

  Commercially available styrene-isoprene block copolymers include Quintac 3421, Quintac 3620, Quintac 3433N, Quintac 3520, Quintac 3450, Quintac 3270, Quintac 3280, Quintac 3390 manufactured by Nippon Zeon. (Trade name), D1107P, D1111, D1112P, D1113P, D1114PX, D1117P, D1119P, D1124P, D1128PX, D1193P, D4433P (trade name) manufactured by Kraton Polymer, TSRC, vector 4111A, vector 4111N, vector 4113A, vector 4113N, vector 4114A, vector 4114N, vector 4186A, vector 4187A, vector 4211A, vector 4211N, As a commercial product of the terter 4213A, the vector 4213N, the vector 4215A, the vector 4230, the vector 4293A, the vector 4411A (trade name) and the styrene-butadiene block copolymer, D1101, D1102, D1116, D1118, D1122 manufactured by Kraton Polymer Co., Ltd. D1133, D1144, D1184, D4141, D4150, D4158 (trade names) Vector 2336, Vector 2411, Vector 2411P, Vector 2518, Vector 2518A, Vector 2518LD, Vector 2518P, Vector 2518PC, Vector 2518PC, Vector, manufactured by TSRC 7400, vector 8508, vector 8508A, tie pole 3201, tie pole 3206, tie pole 4202, Pole 4230, Typole 4270 (trade name), Asahi Kasei Chemicals Tuffprene A, Taffeprene 125, Taffeprene 126S, Taffeprene 315P, Asaprene T411, Asaprene T412, Asaprene T413, Asaprene T420, Asaprene T436, Asaprene T436, Asaprene T436 T438, Asaprene T439 (trade name) and the like. Examples of commercially available hydrogenated styrene-isoprene block copolymers include G1701, G1702, G1750X, G1765X, G1780X (trade names) manufactured by Kraton Polymer, Septon 1001, Septon 1020, Septon 2002, and Septon 2004 manufactured by Kuraray. , Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104 (trade name), and the like. Commercially available products of hydrogenated styrene-butadiene block copolymers include G1643, G1645, G1650, G1651, G1652, G1657, G1657, G1726 (trade names) manufactured by Kraton Polymer, and Septon 8004 and Septon 8006 manufactured by Kuraray. Septon 8007, Septon 8076, Septon 8104 (trade name), TSRC tie pole 6150, tie pole 6151, tie pole 6152, tie pole 6154, tie pole 6159 (trade name), Asahi Kasei Chemicals H1221, H1062 , H1052, H1041, H1051, H1057, H1043, N504 (trade name), and the like. Examples of commercially available hydrogenated styrene-butadiene-isoprene block copolymers include Kuraray's Septon 4033, Septon 4044, Septon 4055, Septon 4077, and Septon 4099 (trade name).

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

Other rubbers are not particularly limited. For example, natural rubber; isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, propylene-butylene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic Examples thereof include synthetic rubbers such as rubber and polypentenamer rubber. Among these, natural rubber is preferable from the viewpoint of crosslinkability and economy.
By using natural rubber, the crosslinkability of the adhesive composition is further improved, and the economy tends to be excellent.

  When natural rubber is contained, the content thereof is preferably 3 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 100% by mass of the adhesive composition. -75 mass%. 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, the polymer other than the preferred component (A) and component (B) according to the application and performance will be described more specifically.

(Hydrogenated aromatic vinyl elastomer)
Adhesive composition is stuck to the adherend and the adhesive residue is reduced when it is peeled off, or the adhesive strength of adhesive composition is suppressed over time or creep property (smaller value is better), From the viewpoints of heat resistance and weather resistance, a hydrogenated aromatic vinyl elastomer can be used. Although it does not specifically limit as hydrogenated aromatic vinyl type elastomer, For example, hydrogenated styrene-butadiene type block which has structures, such as S-EB-S (S: polystyrene block, EB: ethylene / butylene copolymer block) Copolymer; Hydrogenated styrene-isoprene block copolymer having a structure such as S-EP-S (S: polystyrene block, EP: ethylene / propylene copolymer block); S-EEP-S (S: polystyrene) Examples thereof include a hydrogenated styrene-butadiene-isoprene block copolymer having a structure such as a block and EEP: ethylene / ethylene / propylene copolymer block). Of these, hydrogenated styrene-butadiene block copolymers and hydrogenated styrene-isoprene block copolymers are preferred.

  The styrene content of the hydrogenated aromatic vinyl elastomer is preferably 10% by mass to 45% by mass, more preferably 13% by mass to 40% by mass with respect to 100% by mass of the hydrogenated aromatic vinyl elastomer. More preferably, it is 15 mass%-35 mass%.

  The polystyrene block content of the hydrogenated aromatic vinyl elastomer is preferably 30% by mass or less, more preferably 21% by mass or less, with respect to 100% by mass of the hydrogenated aromatic vinyl elastomer. More preferably, it is 15 mass% or less. When the content of the polystyrene block is within the above range, flexibility and compatibility tend to be further improved.

  Further, the content of B in the ethylene / butylene copolymer block in the hydrogenated aromatic vinyl elastomer is preferably high, and preferably 35 mol% or more with respect to 100 mass% of the hydrogenated aromatic vinyl elastomer. More preferably, it is 45 mol% or more, More preferably, it is 55 mol% or more, Especially preferably, it is 60 mol% or more. When the content of B in the ethylene / butylene copolymer block is within the above range, flexibility and compatibility tend to be further improved.

  The hydrogenation rate of the unsaturated double bond based on the conjugated diene compound in the hydrogenated aromatic vinyl elastomer is preferably more than 90 mol%.

(Other partially hydrogenated aromatic vinyl elastomers)
From the viewpoint of adjusting the cohesive strength, adhesive strength, tack, and T (ODT) (order-disorder transition temperature) of the adhesive composition, it is preferable to use other partially hydrogenated aromatic vinyl elastomers. The melt viscosity can be adjusted by adjusting T (ODT) (order-disorder transition temperature). The other partially hydrogenated aromatic vinyl elastomer includes a polymer block mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block mainly composed of at least one conjugated diene compound. The hydrogenation rate H (%) of the unsaturated double bond based on the above is 5 to 90 mol%, and the maximum value of the loss coefficient tan δ from −100 ° C. to 0 ° C. is less than 0.4.

(Non-hydrogenated aromatic vinyl elastomer)
As the adhesive composition, a non-hydrogenated aromatic vinyl elastomer may be used from the viewpoint of imparting high flexibility and high adhesiveness and suppressing gelation, or high economic efficiency. . Although it does not specifically limit as a non-hydrogenated aromatic vinyl-type elastomer, For example, a styrene-ethylene-type block copolymer; SBS, (SB) _nX (S: Polystyrene block, B: Polybutadiene block) , X: residue of coupling agent), etc .; styrene-butadiene block copolymer; styrene-propylene block copolymer; S-I-S, (S-I) _n X (S: polystyrene) Styrene-isoprene block copolymer having a structure such as block, I: polyisoprene block, X: residue of coupling agent); (S- (I / B)) _n X, S- (I / B) -S (S: polystyrene block, I / B: isoprene / butadiene copolymer block (isoprene and butadiene may be alternately mixed at an arbitrary ratio; Butadiene - - isoprene block copolymers of styrene having a structure such as residues of a coupling agent): may not be constant), X. Among _{this, (S-I) n X} , (S-B) n X, (S- (I / B)) n X is preferably, and more preferably has 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 with respect to 100% by mass of the non-hydrogenated aromatic vinyl elastomer.

  In addition, the content of the non-hydrogenated aromatic vinyl elastomer diblock (for example, SB, SI, SBX, SIX) is determined based on the nonhydrogenated aromatic vinyl elastomer 100. Preferably it is 10-80 mass% with respect to the mass%.

(Isoprene block copolymer)
As the adhesive composition, an isoprene-based block copolymer having a non-hydrogenated isoprene monomer unit may be used from the viewpoint of imparting excellent tack or economical efficiency. The isoprene-based block copolymer is not particularly limited. For example, (SI) n, (SI) n-S, (SI) nX (S: polystyrene block, I: polyisoprene block, n: An integer of 1 or more, preferably an integer of 1 to 6, and a styrene-isoprene block copolymer having a structure such as X: a residue of a coupling agent) is preferable. 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 with respect to 100% by mass of the isoprene-based block copolymer. Or less, more preferably 18% by mass or less.

(Conjugated diene synthetic rubber)
From the viewpoints of workability, low melt viscosity at 180 ° C. or lower, good tack and adhesion, adhesiveness, and die-cutting properties, a conjugated diene synthetic rubber can be used. The conjugated diene synthetic rubber is not particularly limited, and examples thereof include isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, and propylene-butylene rubber.

  In addition, as a pressure-sensitive adhesive composition for pressure-sensitive adhesive tapes, polybutadiene rubber or polyisoprene rubber may be used from the viewpoint of improving the self-back surface adhesive strength and skin adhesive strength. Among these, polyisoprene rubber is more preferable. The addition amount of the polybutadiene rubber and the polyisoprene rubber is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and further preferably 5 to 5% by mass with respect to 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, the self-back adhesive force and the skin sticking force tend to be further improved. Moreover, 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 adhesive residue tends to be further suppressed.

  As the conjugated diene-based synthetic rubber, a conjugated diene-based diblock copolymer is used from the viewpoints of workability of the adhesive composition, low melt viscosity at 180 ° C. or less, good tack and adhesive strength, and adhesiveness. May be. Although it does not specifically limit as a conjugated diene type diblock copolymer, For example, the polymer which has structures, such as SI, (SI) X, SB, (SB) X, these hydrogen An additive is mentioned. These may be used alone or in combination of two or more, and may be liquid or solid at room temperature.

  The content of the conjugated diene synthetic rubber is preferably 3 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 75% with respect to 100% by mass of the adhesive composition. % By mass. When the content of the conjugated diene synthetic rubber is within the above range, the oil bleed resistance, low melt viscosity, tack, adhesion, adhesiveness, and flexibility of the adhesive composition tend to be further improved. .

(Ionomer)
If the adhesive composition requires high low-temperature coating properties, low creep performance, high strength or high elongation, the polymer may be used in the ionomer state. Although it does not specifically limit as an ionomer, For example, the homopolymer or copolymer containing the carboxylate, sulfonate, or phosphonate neutralized by a metal ion or partially neutralized is preferable. The content of the ionomer is preferably 5% by mass or less with respect to the total amount of the adhesive composition.

(Polyolefin resin)
From the viewpoint of giving high-temperature storage stability and high elongation as the adhesive composition, or reducing the amount of tackifying resin in the adhesive composition (55 mass% or less in the composition, further 45 mass) % Or less), high fluidity, improvement of fluidity and adhesive properties, economy, etc., polyolefin resins can be used. Although it does not specifically limit as polyolefin-type resin, For example, it is preferable to use the copolymer of an alpha olefin and an olefin, or a propylene homopolymer. The melting point (conditions: DSC measurement, 5 ° C./min) of these polymers is preferably 110 ° C. or less, more preferably 100 ° C. or less, and further preferably 60 ° C. to 90 ° C. These polymers may be resins or elastomers. Commercially available polyolefin-based elastomers are not particularly limited, but include AFFINITY and AFFINITY GA (trade name) manufactured by Dow Chemical Company, Vistamaxx (trade name) manufactured by ExxonMobil Chemical Company, and the like. AFFINITY GA1875, GA1900, GA1000R, GA1950, EG8185, EG8200G, PL1280G and the like are preferable.

  Further, from the viewpoint of creep performance (smaller value is better), an olefin-based elastomer having a block is more preferable. The molecular weight distribution of these polymers is preferably 1 to 4, more preferably 1 to 3. Moreover, it is more preferable to use 2 or more types of this polymer together from a viewpoint of workability. Specifically, it is preferable to use 30,000 to 60,000 and 60,000 to 90,000 polymers in combination, and at least 3,5,000 to 5,5,000 and 60,000 to 80,000 polymers. It is more preferable to use together.

(Liquid component)
The adhesive composition using a polyolefin resin preferably contains a liquid component (oil or the like). Content of a liquid component becomes like this. Preferably it is 20 mass% or more with respect to 100 mass% of adhesive compositions, More preferably, it is 25 mass% or more. Moreover, when elongation is required, it is preferable to use an olefin elastomer together, and it is more preferable to use an olefin elastomer having Tg at -10 ° C or lower.

(wax)
The adhesive composition may contain a wax as necessary. The addition amount of the wax is preferably 20% by mass or less, more preferably 2 to 10% by mass, and further preferably 5 to 10% by mass with respect to 100% by mass of the adhesive composition. When the addition amount of the wax is within the above range, the melt viscosity, particularly the melt viscosity at 140 ° C. or lower tends to be further reduced.

  The wax is not particularly limited, and examples thereof include paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. By using such a wax, the melt viscosity, particularly the melt viscosity at 140 ° C. or lower tends to be further reduced.

  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. The melting point of the wax is preferably 110 ° C. or less. When the melting point of the wax is within the above range, the melt viscosity, particularly the melt viscosity at 140 ° C. or lower tends to be further reduced.

  The softening point of the tackifier used in combination with the wax is preferably 70 ° C. or higher, more preferably 80 ° C. or higher. G ′ (measuring condition: 25 ° C., 10 rad / s) of the adhesive composition obtained in this case is preferably 1 Mpa or less, and the crystallization temperature is preferably 7 ° C. or less.

  As waxes that can be used, commercially available product names “115”, product name “120”, product name “125”, product name “130”, product name “135”, 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 " , Product name “Hi-Mic-1080”, product name “Hi-Mic-1090”, product name “Hi-Mic-2045”, product name “Hi-Mic-2065”, product name “Hi-Mic-2095” "Ultrasen 7A55A" manufactured by Tosoh Corporation, trade name "A-C540", trade name "A-C540A", trade name "A-C580", trade name "A-C5120", trade name, manufactured by Honeywell. “A-C400”, product name “A-C400A”, product name “A-C405 (S)”, product name “A-C405 (M)”, product name “A-C405 (T)”, product name “ A-C645P ”, trade name“ A-C573A ”, trade name“ A-C573P ”, and the like.

(Polar group-containing polymer)
The adhesive composition may contain a polar group-containing polymer containing an atom selected from the group consisting of nitrogen, oxygen, silicon, phosphorus, sulfur, tin and the like, if necessary. The polar group-containing polymer is not particularly limited. For example, a so-called modified polymer bonded to a block copolymer, or a modified block copolymer obtained by modifying a block copolymer component with a modifying agent such as maleic anhydride. And oils whose side chains and terminals are modified with amines, epoxies, carboxylic acids, carboxylic acid anhydrides, and the like. By using a polar group-containing polymer, a highly water-absorbing polymer (SAP), a resin such as acrylic resin, vinyl chloride, nylon, or a cross-linked product thereof, and an adherend having a high SP value such as glass, metal, etc. There exists a tendency for an adhesive property to improve more. Commercially available products include HG252 (trade name) manufactured by Kuraray Co., Ltd., M1943, M1911, M1913, MP10, Tuffprene 912 (trade name) manufactured by Asahi Kasei Chemicals, and Typol 7131 (trade name) manufactured by TSRC. .

(Stabilizer)
The adhesive composition may contain a stabilizer as necessary. `` Stabilizer '' is formulated to improve the stability of the hot melt adhesive by preventing the molecular weight reduction, gelation, coloring, generation of odor, etc. due to heat of the hot melt adhesive, There is no particular limitation.

  Examples of the stabilizer include an antioxidant and a light stabilizer. Antioxidants and light stabilizers are generally used for disposable products, and can be used as long as they can obtain the intended disposable products described below, and are particularly limited. is not.

(Antioxidant)
“Antioxidants” can be used, for example, to prevent oxidative degradation of hot melt adhesives. The antioxidant is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t- Butylphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) Methyl] -0-cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6 -[1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] acrylate Phenolic antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-tetrakis (β-lauryl thiopropionate) and other antioxidants; tris (nonylphenyl) phosphite And phosphorus-based antioxidants such as tris (2,4-di-t-butylphenyl) phosphite. These may be used alone or in combination of two or more.

  Specific examples of commercially available antioxidants include Sumitizer GM (trade name) manufactured by Sumitomo Chemical Co., Ltd., Sumilyzer TPD (trade name) and Smither TPS (trade name), Irganox manufactured by Ciba Specialty Chemicals. 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 Johoku Chemical Co., Ltd. be able to.

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

(Light stabilizer)
A “light stabilizer” can be used, for example, to improve the light resistance (low change in adhesive properties after UV irradiation) of a hot melt adhesive. The light stabilizer is not particularly limited. For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzo Benzotriazole ultraviolet absorbers such as triazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole; benzophenones such as 2-hydroxy-4-methoxybenzophenone UV absorbers; triazine UV absorbers; hindered amine light stabilizers; lactone stabilizers: HALS and the like. These may be used alone or in combination of two or more.

  Specific examples of commercially available light stabilizers include Tinuvin P (trade name), Tinuvin 770DF (trade name), Cimasorb2020FDL (trade name) manufactured by BASF, Adeka Stub LA-52 (trade name) manufactured by ADEKA, and Adeka Stub LA. -57 (trade name) and ADK STAB LA-77Y (trade name) can be exemplified.

The light stabilizer content 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 0.07% by mass in terms of high light resistance. The above is more preferable.
In addition, the light fastness content in the adhesive composition of the present embodiment is preferably 1% by weight or less, more preferably 0.5% by weight or less, in terms of suppression of bleeding of the light fastness agent and economical efficiency. 0.3 mass% or less is more preferable.
From the viewpoint of higher light resistance, it is preferable to use the above antioxidant together with the above light stabilizer.
Among antioxidants, it is preferable to use at least a phosphorus-based antioxidant in addition to the above-mentioned light-resistant agent in terms of higher light resistance.
As antioxidant content in the adhesive composition of this embodiment, 0.02 mass% or more is preferable at the point of high light resistance, 0.04 mass% or more is more preferable, 0.06 mass % Or more is more preferable.
In addition, the light resistance content in the adhesive composition of the present embodiment is preferably 1.5% by mass or less, preferably 1.0% by mass or less, in terms of suppression of bleeding of the antioxidant and economical efficiency. Is more preferable.

(Fine particle filler)
The adhesive composition may contain a fine particle filler as required. The fine particle filler is not particularly limited. For example, mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, zinc white, activated zinc white plasma magnesium carbonate, Examples thereof include silica gel hydroxide, diatomaceous earth, and barium sulfate. These shapes are preferably spherical, and the dimensions (diameter in the case of a spherical shape) are not particularly limited.

[Characteristics of adhesive composition]
The performance of the adhesive composition of this embodiment can be measured according to the measurement conditions shown in the Examples, using pressure-sensitive adhesive tapes produced under the conditions shown in the Examples described later.

  G ′ (measurement condition: 25 ° C., 10 rad / s) of the adhesive composition is preferably 20000 or less, more preferably 15000 or less. When G ′ of the adhesive is within the above range, the adhesive residue of the adhesive composition tends to be further reduced.

  The content of the liquid diluent is preferably 60% by mass or less with respect to 100% by mass of the adhesive composition. When the content of the liquid diluent is within the above range, it is particularly useful for the skin application of an adhesive including transdermal drug delivery.

  The adhesive composition of this embodiment can also be used for paper processing, bookbinding, disposable products, and the like. Among these, since it is excellent in adhesion in a wet state, it is suitable for a disposable product. Disposable products are woven fabric, non-woven fabric, rubber, resin, paper, polyolefin film, polyester film, PVC film, ionomer film, PVDC film, PVA film, PC film, PS film, PAN film, PEN film, cellophane film, nylon The adhesive composition can be formed by solution coating or hot melt coating on at least one member selected from the group consisting of a film, a polyimide film, an EMAA film, and an EVOH film. The polyolefin film is preferably a polyethylene film or a polypropylene film for reasons such as durability and cost. The paper is preferably kraft paper or high-quality paper for reasons such as durability and cost, and is preferably kraft paper laminated with polyethylene from the viewpoint of durability and water resistance.

  The melt viscosity at 150 ° C. of the hot melt adhesive for disposable products for sanitary materials is preferably 5000 mPa.s. s or less, more preferably 400 to 3500 mPa.s. s, more preferably 800 to 3000 mPa.s. s. The melt viscosity is the viscosity of the hot melt adhesive and is measured with a Brookfield RVT viscometer (spindle No. 27). When the melt viscosity is in the above range, the hot melt adhesive is suitable for low temperature coating, and moreover, it is evenly applied to non-woven fabric and easily penetrates. It is suitable for.

  Although it does not specifically limit as a disposable product for sanitary materials, For example, a paper diaper, a sanitary napkin, a pet sheet, a hospital gown, a lab coat, etc. are mentioned.

[Method for producing adhesive composition]
The adhesive composition of this embodiment mixes the hydrogenated block copolymer composition described above, a tackifier, a softener, and other components as required by a known method. Can be manufactured. Although it does not specifically limit as a mixing method, For example, the method of mixing uniformly a block copolymer composition, a tackifier, and a softener, heating with a mixer or a kneader etc. is mentioned.

  The temperature at the time of mixing becomes like this. Preferably it is 130 to 220 degreeC, More preferably, it is 140 to 210 degreeC, More preferably, it is 150 to 200 degreeC. When the mixing temperature is 130 ° C. or higher, the block copolymer composition can be sufficiently melted and the dispersion tends to be good. Moreover, when the temperature at the time of mixing is 220 degrees C or less, it exists in the tendency which can prevent evaporation of the low molecular-weight component of a crosslinking agent or a tackifier, and deterioration of an adhesive property.

[Method of applying adhesive composition]
When the adhesive composition is applied and used, the application method is not particularly limited as long as the target product can be obtained. For example, the adhesive composition is dissolved in a solvent. Examples thereof include a solution coating method and a hot melt coating method in which the adhesive composition is melted and applied.

  Among these, the hot melt coating method is preferable in view of environmental pollution and ease of coating. Hot melt coating methods are roughly classified into contact coating and non-contact coating. “Contact application” refers to an application method in which an ejector is brought into contact with a member or a film when a hot melt adhesive is applied. In addition, “non-contact coating” refers to a coating method in which a jetting machine is not brought into contact with a member or a film when a hot melt adhesive is applied. The contact coating method is not particularly limited, and examples thereof include slot coater coating and roll coater coating, die coating, porous coating applied in a porous manner, and pattern coating. In addition, the non-contact coating method is not particularly limited, for example, spiral coating that can be applied spirally with air by intermittent or continuous coating, omega coating or control seam coating that can be applied in a wave shape, surface Slot spray coating or curtain spray coating that can be applied in the form of dots, dot coating that can be applied in the form of dots, bead coating that can be applied in the form of a line, forming melt coating that foams hot melt, coating on thread-like materials And spray coating that coats in the form of a mist.

  Conventional hot melt adhesives with poor thermal stability easily phase separate components in a high temperature tank. Phase separation also causes clogging of tank filters and transportation piping. In this respect, the adhesive composition of the present embodiment has good thermal stability, is uniformly melted in a high-temperature tank at 100 to 220 ° C., and phase separation is suppressed.

In a production line for disposable products for sanitary materials, a hot melt adhesive is generally applied to various members (for example, tissue, cotton, nonwoven fabric, polyolefin film, etc.) of disposable products. At the time of application, the hot melt adhesive may be ejected from various ejectors.
Hot melt adhesives for disposable products for sanitary materials are suitable for spiral coating. The ability to apply a hot melt adhesive with a wide width by spray coating is extremely useful for producing disposable products. A hot melt adhesive that can be applied with a wide width can be adjusted to have a narrow coating width by adjusting the pressure of hot air.

  If the hot melt adhesive is difficult to apply due to its wide width, a large number of spray nozzles are required to obtain a sufficient adhesion area. It is also unsuitable for producing disposable products. In this regard, the adhesive composition of the present embodiment is suitable as a disposable product for sanitary materials because it can be spirally applied with a wide width.

  Since the adhesive composition of this embodiment has good coating suitability at 150 ° C. or less, it is useful for producing disposable products for sanitary materials. When the hot melt adhesive is applied at a high temperature, the polyolefin (preferably polyethylene) film that is the base material of the disposable product is melted or thermally contracted, 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 nonwoven fabric, which is the base material of the disposable product, hardly changes, and the appearance of the product is not impaired.

  Since the adhesive composition of this embodiment is excellent in high-speed coating suitability, it is suitable for producing disposable products for sanitary materials in a short time. When a hot melt adhesive is applied to a substrate conveyed at high speed, the contact-type coating method may cause the substrate to break due to friction. Since the adhesive composition of this embodiment is suitable for spiral coating which is a kind of non-contact coating, it is suitable for high-speed coating and can improve the production efficiency of disposable products. Furthermore, the adhesive composition of this embodiment suitable for high-speed coating does not disturb the coating pattern.

<Manufacturing method of adhesive tape / label>
The method for producing the adhesive composition of the present embodiment is not particularly limited, and each of the hydrogenated block copolymer, the tackifier resin, and other block copolymers and oils as necessary. A method of uniformly mixing the components at a predetermined blending ratio while heating them with a known mixer, kneader, single screw extruder, twin screw extruder, Banbury mixer or the like can be mentioned.

The adhesive composition of the present embodiment is preferably used by being laminated on at least a substrate. There is no limitation in the kind of base material, For example, the film which consists of thermoplastic resins, and non-thermoplastic base materials, such as paper, a metal, a woven fabric, a nonwoven fabric, can also be used.
When used as a masking material during paint repainting work, it is preferable to use a metal foil such as an aluminum foil as a base material from the viewpoint of suppressing corrosion by a chemical solution.

  Moreover, when using for sanitary goods, it is good also as an elastic laminated body which laminated | stacked the adhesive composition layer and the elastomer layer on this nonwoven fabric on a nonwoven fabric as a base material. In order to obtain excellent fit, it is preferable that the stretchable laminate has a residual strength ratio at 100% elongation of 80% or more and a residual strength ratio at 50% elongation of 70% or more.

A release agent may be added to or applied to the base material. Examples of the release agent include a long-chain alkyl release agent and a silicon release agent. In addition to the substrate, a release layer may be further provided.

When higher weather resistance (low adhesive force change after UV irradiation) is required, it is more preferable to use a substrate or a release layer having a low ultraviolet transmittance, and the transmittance is more preferably 1% or less.
Further, from the viewpoint of suppressing oxidative degradation due to UV irradiation, it is preferable to use a substrate or a release layer having a low oxygen transmission coefficient, and an oxygen transmission coefficient of 10,000 (cc · 20 μ / m ² at 20 ° C. under dry conditions). · Day · atm) or less, preferably 1,000 (cc · 20µ / m ² · day · atm) or less, more preferably 500 (cc · 20µ / m ² · day · atm) or less. More preferably.

  Although it does not specifically limit as a method of apply | coating the adhesive composition of this embodiment to a base material, For example, T-die coating method, roll coating method, multi-bead coating method, spray coating method, etc. are mentioned. . Further, either an extrusion coating (hot melt coating) method or a spread coating method may be used, but the adhesive coating composition of this embodiment is suitable for an extrusion coating method having high heat aging resistance and high economic efficiency. .

[Use]
The adhesive composition of this embodiment has good solubility and coating properties, ejection stability, surface skin, excellent tackiness and adhesive strength, and a good balance of these adhesive properties. is there. Taking advantage of these features, various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, surface protective sheets and films, various lightweight plastic molded product back glue, carpet fastening back glue, tile fastening back glue Can be used for adhesives, etc., especially for adhesive tapes, adhesive sheets / films, adhesive labels, surface protection sheets / films, hygiene materials, etc. be able to.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, the properties and physical properties of the polymers were measured by the following methods.

[(1): Characteristics of hydrogenated block copolymer]
<(1-1) Weight average molecular weight>
The weight average molecular weight of the hydrogenated block copolymer is based on the molecular weight of the peak of the chromatogram using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurement of commercially available standard polystyrene. Asked. When the hydrogenated block copolymer includes a hydrogenated block copolymer having two different structures of component (A) and component (B), the peak having the smallest weight average molecular weight is represented by component (A) and component (A ) Followed by the peak having the largest weight average molecular weight as component (B). The component (A) and the component (B) have a value obtained by dividing the peak area of each component by the total peak area ((peak area of the component (A) or component (B)) / (total peak area)). It is assumed that it is 1 or more. HLC-8320EcoSEC collection was used as measurement software, and HLC-8320 analysis was used as analysis software. The peak area was measured by the method described later.
(Measurement condition)
GPC: HLC-8320GPC (manufactured by Tosoh Corporation)
Detector; RI
Detection sensitivity: 3 mV / min Sampling pitch: 600 msec
Column: 4 TSKgel superHZM-N (6 mm ID × 15 cm) (manufactured by Tosoh Corporation)
Solvent: THF
Flow rate; 0.6 mm / min Concentration; 0.5 mg / mL
Column temperature: 40 ° C
Injection volume: 20 μL

<Content of (1-2) vinyl aromatic hydrocarbon monomer unit (styrene)>
A certain amount of hydrogenated block copolymer is dissolved in chloroform, and using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450), an absorption wavelength (styrene) due to the vinyl aromatic compound component (styrene) in the solution ( 262 nm) peak intensity was measured. From the obtained peak intensity, the content of the vinyl aromatic hydrocarbon monomer unit (styrene) was calculated using a calibration curve.

<(1-3) Vinyl bond amount in conjugated diene monomer unit and hydrogenation rate of conjugated diene monomer unit>
By adding a large amount of methanol to the reaction solution after the hydrogenation reaction, the block copolymer before hydrogenation and the hydrogenated block copolymer were precipitated and recovered. Next, the hydrogenated block copolymer was extracted with acetone, and the hydrogenated block copolymer was vacuum dried. This was used as a sample for 1H-NMR measurement, and the hydrogenation rate and the amount of vinyl bonds were measured. The conditions for 1H-NMR measurement are described below.
(Measurement condition)
Measuring instrument: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Extracted sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

<(1-4) Average molecular weight of polymer block (Ar) mainly composed of vinyl aromatic hydrocarbon monomer unit>
The average molecular weight of the polymer block (Ar) is calculated from 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. Asked.
(Weight average molecular weight of hydrogenated block copolymer) × (Average content (% by mass) of polymer block (Ar) in hydrogenated block copolymer) / 100 = (vinyl aromatic hydrocarbon monomer unit) The average molecular weight of the polymer block (Ar) mainly composed of

“Average content (mass%) of polymer block (Ar) in hydrogenated block copolymer” means that the number of polymer blocks (Ar) contained in the hydrogenated block copolymer is one. Means the content of the block and, when there are two or more polymer blocks (Ar), the average content of those blocks. The average content (mass%) of the polymer block (Ar) in the hydrogenated block copolymer is the content of vinyl aromatic hydrocarbon monomer units, the vinyl aromatic hydrocarbon of the hydrogenated block copolymer. It can be calculated as follows from the number of polymer blocks (Ar) mainly composed of monomer units.
(Average content (mass%) of polymer block (Ar) in hydrogenated block copolymer) = (Content of vinyl aromatic hydrocarbon monomer unit contained in hydrogenated block copolymer (mass fraction) )) ÷ (number of polymer blocks (Ar) mainly composed of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer)
(Note that when the hydrogenated block copolymer contains the component (A) and the component (B), the value calculated as described above using the weight average molecular weight of each component will be adopted.)

<Contents of (1-5) Component (A) and Component (B)>
When a hydrogenated block copolymer having two different structures of component (A) and component (B) is included as the hydrogenated block copolymer, the total peak area of the elution curve measured in (1-1) above. The ratio of the peak area of the component (A) was defined as the content of the component (A). Moreover, the ratio of the peak area of the component (B) with respect to the total peak area of the elution curve measured by said (1-1) was made into content of the component (B). In addition, about area ratio, it calculated | required by the vertical division | segmentation in the inflection point of each curve between peaks using analysis software HLC-8320 analysis.

<(2): Method for measuring physical properties of hydrogenated block copolymer composition obtained in Production Example>
<(2-1) Measurement of metal compound (metal amount) in terms of metal atom>
The amount of metal contained in the hydrogenated block copolymer composition obtained in the following production example was determined using inductively coupled plasma (ICP, Inductive Coupled Plasma, manufactured by Shimadzu Corporation, apparatus name: ICPS-7510). It was measured. First, the hydrogenated block copolymer is completely dissolved in sulfuric acid and nitric acid, an aqueous solution containing a metal component is sprayed into argon plasma, and the intensity of the wavelength of light unique to each metal element emitted from it is measured. The amount of metal contained in 100 parts by mass of the hydrogenated block copolymer composition was determined by a calibration curve method.

<(2-2) Measurement of particle size (particle size distribution)>
The particle diameter of the metal compound particles contained in the hydrogenated block copolymer composition obtained in the production example described later is measured by the following method using a laser diffraction particle size distribution meter (LA-300, manufactured by HORIBA). did.

  The cyclohexane solution of the hydrogenated block copolymer composition is dropped into a circulation bath in which cyclohexane is circulated, and the particle size is measured under the following conditions by controlling the circulation concentration so that the transmittance is in the range of 70 to 98%. went.

In addition, when the hydrogenated block copolymer composition contains a metal other than the titanium compound, the average particle size obtained by the following method is the particle size of the entire metal compound particle containing the titanium compound and the other metal compound. is there.
[Measurement condition]
Measurement method: Mie scattering theory Measurement range: 0.1-600 μm
Measurement time: 20 sec
Light source: 650 nm Semiconductor laser 5 mW
Data read count: 5-10 times Measurement temperature: 25 ° C

Here, the average particle diameter is an arithmetic average diameter, is a value obtained by arithmetically averaging the 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 J-th particle size range (μm)

  In addition, the content of the titanium compound having a particle size of 0.1 μm to 50 μm in the titanium compound, the content of the titanium compound having a particle size of 0.1 μm to 100 μm, and the average particle size of the titanium compound are LA -Calculated from accumulated passage in 300 software.

<(2-3) State analysis of metal component in hydrogenated block copolymer composition>
Using the X-ray diffractometer XRD (Rigaku Corporation Ultra-IV (Cu tube)) as the metal component contained in the hydrogenated block copolymer composition obtained in the production example described below, excitation voltage: Current = 40 kV: 40 mA, slit DS = 1 degree, SS open, RS open, longitudinal slit 10 mm, scan range 2θ = 5-65 degrees (0.02 degrees / step), scan speed 1-10 degrees / minute Analysis was carried out. This analyzed the state of the titanium compound contained in the polymer.

[(3): Measurement of physical properties of adhesive composition]
(Preparation of adhesive composition)
100 parts by mass of hydrogenated block copolymer, 200 parts by mass of Quinton R100 (made by Nippon Zeon Co., Ltd.) as a tackifier, and 100 parts by mass of PW-90 (made by Idemitsu Kosan Co., Ltd.) as a softener , Were mixed. The mixture is melt-kneaded with a mixer (model: L5M-A, Silverson Nippon Co., Ltd., four paddle type blades) at 180 ° C. for 60 minutes while being heated using an oil bath, and hot-melt adhesive An agent composition was obtained.

  In the adhesive composition, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- 5) is used as a stabilizer with respect to 100 parts by mass of the hydrogenated block copolymer composition. 1 part by mass of methylbenzyl) -4-methylphenyl acrylate was added.

(Evaluation of adhesive composition)
<(3-1) Melt viscosity of adhesive composition>
The melt viscosity of the adhesive composition was measured with a Brookfield viscometer (DV-III manufactured by Brookfield) at a temperature of 180 ° C. Based on the obtained value, the melt viscosity was evaluated according to the following criteria. Evaluation is ◎, ○, △, × from the good order.
Melt viscosity (180 ° C.) (mPa · s) ≦ 1500: ◎
1500 <melt viscosity (180 ° C.) (mPa · s) ≦ 4500: ○ 4500 <melt viscosity (180 ° C.) (mPa · s) ≦ 8000: Δ
8000 <melt viscosity (180 ° C.) (mPa · s): ×

<Die-cutting property evaluation of (3-2) adhesive composition>
The adhesive composition was molded into a sheet having a thickness of 1 cm and cut out to have a size of 5 cm × 5 cm. Immediately after wiping the scissors blade with gauze moistened with ethanol, the cut adhesive composition was scissored. Based on the obtained results, the die cut property was evaluated according to the following criteria. The evaluation shall be ○ and × from the good order.
When the adhesive composition does not remain in the bag: 〇 When the adhesive composition remains in the bag: ×

(Production of adhesive tape)
The melted adhesive composition was cooled to room temperature and dissolved in toluene. The obtained toluene solution is coated onto a PET film with an applicator, and then kept at room temperature for 30 minutes and in an oven at 70 ° C. for 7 minutes to completely evaporate the toluene and produce an adhesive tape with an adhesive layer thickness of 30 μm. did. The obtained adhesive tape was used in the following evaluation.

(Evaluation of adhesive tape α)
<(3-3) Holding power of adhesive composition>
Adhesive tape was applied so that the area of 15 mm × 25 mm was in contact with the SUS plate, and a load of 1 kg was applied at 50 ° C., and the time until the adhesive tape slipped was measured. Based on the obtained time, the holding power of the adhesive composition was evaluated according to the following criteria. Evaluation will be ☆, ◎, ○, △, × from the good order.
40 ≦ holding force (min): ☆
20 ≦ holding force (minutes) <40: ◎
5 ≦ holding force (min) <20: ○ 2 ≦ holding force (min) <5: Δ
Holding power (minutes) <2: ×

<(3-4) Tack of adhesive composition>
The probe tack of the adhesive composition was measured according to ASTM D2979. After sticking the adhesive tape on the weight (load 10 g) at a temperature of 23 ° C., the probe (5 mmφ) is brought into contact with the adhesive tape at a speed of 1 mm / sec, and after contacting for 1 second, the speed is 1 mm / sec. The probe was peeled off. The maximum value at this time was measured as a probe tack value, and the tack was evaluated. Evaluation was made into ◎, ○, Δ, and × in the order of goodness.
Probe tack (N / 5mmφ) ≧ 2.0: ◎
2.0> probe tack (N / 5mmφ) ≧ 1.0: ○ 1.0> probe tack (N / 5mmφ) ≧ 0.2: Δ
0.2> probe tack (N / 5 mmφ): ×

(Evaluation of adhesive tape β)
<(3-5) Holding power of adhesive composition>
Adhesive tape was applied so that an area of 15 mm × 15 mm was in contact with the SUS plate, and a load of 1 kg was applied at 50 ° C. to measure the time until the adhesive tape fell off. Based on the obtained time, the holding power of the adhesive composition was evaluated according to the following criteria. Evaluation shall be (circle), (triangle | delta), and x from a favorable order.
150 ≦ holding force (minutes): ○ 50 ≦ holding force (minutes) <150: Δ
Holding power (min) <50: ×

<(3-6) Adhesive composition tack>
The tackiness of the adhesive composition was evaluated by an inclined ball tack according to JIS-Z0237. Specifically, a starting point for placing the hard sphere, a runway (100 mm) following the start point, and a triangular device (tilt angle 30 degrees) having an adhesive surface (100 mm) of the adhesive tape following the runway on the slope, A hard sphere (size: 1/32 to 32/32 inches) was rolled from the starting point above the slope toward the adhesive surface below the slope. A numerical value 32 times the size of the ball stopped on the adhesive surface was called a “ball number”, and the maximum ball number stopped on each adhesive tape was measured. Based on the obtained ball number, the tackiness of the adhesive composition was evaluated according to the following criteria. Evaluation shall be (circle), (triangle | delta), and x from a favorable order.
10 ≦ ball number: ○
3 ≦ Ball number <10: △
Ball number <3: ×

<(3-7) Time-varying property of adhesive composition>
A 25 mm wide adhesive tape was attached to a SUS plate, and a sample (K) that was allowed to stand at 23 ° C. for 12 hours and a sample (L) that was allowed to stand at 60 ° C. for 48 hours were prepared. Peeling was performed at a peeling speed of 300 mm / min, and the 180 ° peeling force at that time was measured. Based on the absolute value of the difference between the peel strength of sample (L) and the peel strength of sample (K), the adhesive strength of the adhesive composition was evaluated according to the following criteria. The evaluation is ◎, ○, Δ, × from the best order.
Difference in peel force (N / 10 mm) <4: ◎
4 ≦ Peeling force difference (N / 10 mm) <8: ○
8 ≦ Peeling force difference (N / 10 mm) <20: Δ
20 ≦ Peeling force difference (N / 10 mm): ×

(Quality evaluation of adhesive tape)
<(3-8) Color tone of adhesive composition>
A 50 mm × 50 mm pressure-sensitive adhesive tape was affixed to white fine paper, and the color tone of the adhesive composition through a PET film was visually evaluated. Based on the obtained results, the color tone of the adhesive composition was evaluated according to the following criteria. Evaluation shall be (circle), (triangle | delta), and x from a favorable order.
If it was white: ○
If neither white nor yellow: △
When yellow is conspicuous: ×

<Dimension controllability of (3-9) adhesive composition>
A 50 mm × 50 mm pressure-sensitive adhesive tape was affixed to white fine paper, sandwiched between two 50 cm × 50 cm × 2 cm glass plates, and allowed to stand in a 60 ° C. gear oven for 3 days. Based on the obtained results, the dimensional controllability of the adhesive composition was evaluated according to the following criteria. Evaluation was made into ○ and × from the good order.
If the edge of the adhesive tape is sticky: ○
If there is no stickiness on the edge of the adhesive tape: ×

[(4) Preparation of hydrogenation catalyst]
In Examples and Comparative Examples described later, a hydrogenation catalyst used for producing a hydrogenated block copolymer was prepared by the following method. A reaction vessel equipped with a stirrer was purged with nitrogen, and 1 L of dried and purified cyclohexane was charged therein. Next, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added. While sufficiently stirring this, an n-hexane solution containing 200 mmol of trimethylaluminum was further added and reacted at room temperature for about 3 days. Thereby, a hydrogenation catalyst was obtained.

[(5) Preparation of hydrogenated block copolymer and hydrogenated block copolymer composition]
<Production Example 1>
A stainless steel autoclave with a stirrer and a jacket with a volume of 40 L was washed, dried, and purged with nitrogen, charged with 5960 g of cyclohexane, and warm water was passed through the jacket to set the content at 65 ° C. 2.0 g of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) and n-butyllithium cyclohexane solution (5.34 g in pure content) were added, and a cyclohexane solution containing styrene (pure content) 335 g) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2370 g in pure content) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Subsequently, a cyclohexane solution containing styrene (335 g in pure content) was continuously added to continue the polymerization. The polymerization conversion of styrene was 100%. After the second stage polymerization of styrene, 2.21 g of methanol was added for inactivation. When the obtained solution was analyzed, the obtained block copolymer had a styrene content of 22% by mass and an average vinyl bond content of the butadiene part of 30 mol%. The weight average molecular weight was 70,000.

  The hydrogenation catalyst prepared as described above was added to the block copolymer solution to carry out a hydrogenation reaction. When the obtained hydrogenated block copolymer solution was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds in the conjugated diene monomer unit in the obtained hydrogenated block copolymer was 75 mol%. It was.

  0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer and mixed well. For the obtained copolymer solution, titanium oxide (manufactured by Junsei Co., Ltd .; rutile type, average particle size 1.5 to 2.1 μm) is converted to 0 per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The mixture was added so as to be 0.02 parts by mass and sufficiently mixed using a lab solution (manufactured by Primics Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 1.

<Production Examples 2 and 4>
Hydrogenation block in the same manner as in Production Example 1 except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent, methanol, and titanium oxide were changed as shown in Table 1, respectively. A copolymer composition was obtained. Table 1 shows the results of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 3>
TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent, and methanol were changed as shown in Table 1, respectively, and then the hydrogenated block copolymer solution was prepared in the same manner as in Production Example 1. Obtained.

  Water in an amount of hydrogenated block copolymer solution: water = 1: 2 (mass ratio) was added to the hydrogenated block copolymer solution and mixed with Lab Solution (manufactured by Primics Co., Ltd.). After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer. On the other hand, 0.3 part by mass was added and mixed 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. Table 1 shows the results of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 5, 5-H>
A stainless steel autoclave with a stirrer and a jacket with a volume of 40 L was washed, dried, and purged with nitrogen, charged with 5960 g of cyclohexane, and warm water was passed through the jacket to set the content at 65 ° C. TMEDA (1.8 g) and n-butyllithium cyclohexane solution (3.85 g in pure content) were added, and a cyclohexane solution containing styrene (360 g in pure content) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2655 g in pure content) 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 cause a coupling reaction. As the coupling agent, Epototo ZX-1059 (Nippon Steel & Sumikin Chemical Co., Ltd.) and cyclohexane mixed at a mass ratio of 90:10 were used. After adding the coupling agent, 0.88 g of methanol was added to inactivate it. When a part of the obtained solution was extracted and analyzed, the obtained block copolymer composition had a styrene content of 12% by mass and an average vinyl bond content of the butadiene part of 35 mol%. In addition, the content of the component (A) in the obtained block copolymer is 40% by mass, the weight average molecular weight is 115,000, the content of the component (B) is 60% by mass, and the weight average The molecular weight was 228,000.

  The hydrogenation catalyst prepared as described above was added to the obtained hydrogenated block copolymer composition solution, and a hydrogenation reaction was performed. A portion of the hydrogenated block copolymer solution was extracted during the hydrogenation reaction and analyzed, and the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound in the resulting hydrogenated block copolymer composition was analyzed. Was 55 mol%. Water in an amount of hydrogenated block copolymer solution: water = 1: 2 (mass ratio) was added to the hydrogenated block copolymer solution and mixed with Lab Solution (manufactured by Primix Co., Ltd.). . Thereafter, silica # 300S-A (manufactured by Chuo Silica Co., Ltd.) was mixed with the polymer solution so as to be 50 ppm in terms of Si atoms, and suction filtered using a filter having a pore size of 2 μm. After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer composition. 0.3 parts by mass was added to the part and mixed 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. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer.

  Further, the hydrogenation reaction of the copolymer solution remaining after the extraction was allowed to proceed completely so that the total hydrogenation rate was 100 mol%. 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer and mixed well. For the obtained copolymer solution, titanium oxide (manufactured by Junsei Co., Ltd .; rutile type, average particle size 1.5 to 2.1 μm) is converted to 0 per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The mixture was added so as to be 0.02 parts by mass and sufficiently mixed using a lab solution (manufactured by Primics Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 5-H. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer composition.

<Production Example 6>
A stainless steel autoclave with a stirrer and a jacket with a volume of 40 L was washed, dried, and purged with nitrogen, charged with 5960 g of cyclohexane, and warm water was passed through the jacket to set the content at 65 ° C. 2.5 g of TMEDA and n-butyllithium cyclohexane solution (5.14 g in pure content) were added, and a cyclohexane solution containing styrene (360 g in pure content) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2655 g in pure content) 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 cause a coupling reaction. As the coupling agent, Epototo ZX-1059 (Nippon Steel & Sumikin Chemical Co., Ltd.) and cyclohexane mixed at a mass ratio of 90:10 were used. After adding the coupling agent, 1.27 g of methanol was added to inactivate it. When a part of the obtained solution was extracted and analyzed, the obtained block copolymer composition had a styrene content of 12% by mass and an average vinyl bond content of the butadiene part of 35 mol%. Further, the content of the component (A) in the obtained block copolymer is 40% by mass, the weight average molecular weight is 80,000, the content of the component (B) is 60% by mass, and the weight average The molecular weight was 160,000.

  The hydrogenation catalyst prepared as described above was added to the obtained hydrogenated block copolymer composition solution, and a hydrogenation reaction was performed. When a part of the copolymer solution was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds 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) propionate was added to 100 parts by mass of the hydrogenated block copolymer composition and mixed well. For the obtained copolymer solution, titanium oxide (manufactured by Junsei Co., Ltd .; rutile type, average particle size 1.5 to 2.1 μm) is converted to 0 per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The mixture was added so as to be 0.02 parts by mass and sufficiently mixed using a lab solution (manufactured by Primics Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 6. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Example 7-B>
A stainless steel autoclave with a stirrer and a jacket with a volume of 40 L was washed, dried, and purged with nitrogen, charged with 5960 g of cyclohexane, and warm water was passed through the jacket to set the content at 65 ° C. 2.6 g of TMEDA and n-butyllithium cyclohexane solution (5.28 g in pure content) were added, and a cyclohexane solution containing styrene (793 g in pure content) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2256 g in pure content) 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 cause a coupling reaction. As the coupling agent, Epototo ZX-1059 (Nippon Steel & Sumikin Chemical Co., Ltd.) and cyclohexane mixed at a mass ratio of 90:10 were used. After adding the coupling agent, 1.53 g of methanol was added to inactivate to obtain a block copolymer solution 7. When a part of the obtained solution was extracted and analyzed, the obtained block copolymer composition had a styrene content of 26% by mass and an average vinyl bond content of the butadiene part of 35 mol%. Further, the content of the component (A) in the obtained block copolymer composition is 70% by mass, the weight average molecular weight is 70,000, and the content of the component (B) is 30% by mass, The weight average molecular weight was 140,000.

  With respect to the block copolymer solution 7, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is 0.3 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer. Added and mixed well. For copolymer solution 7, titanium oxide (manufactured by Junsei Chemical Co., Ltd .; rutile type, average particle size of 1.5 to 2.1 μm) is 0.01 per 100 parts by mass of hydrogenated block copolymer in terms of titanium atoms. It added so that it might become a mass part, and fully mixed using the laboratory solution (made by Primix Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a block copolymer composition of Production Example 7-B. Table 2 shows the results of analyzing the obtained block copolymer composition.

<Production Example 7-1>
A hydrogenation catalyst prepared as described above was added to the block copolymer solution 7 obtained in Production Example 7-B, and a hydrogenation reaction was performed to obtain a hydrogenated block copolymer solution 7-H. . When a part of the hydrogenated block copolymer solution 7-H was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 65 mol%. Met. Hydrogenated block copolymer solution 7-H: Water = 1: 2 (mass ratio) was added in an amount of water to the copolymer solution, and mixed with Lab Solution (manufactured by Primix Co., Ltd.). After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer. On the other hand, 0.3 part by mass was added and mixed 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. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 7-2>
With respect to the hydrogenated block copolymer solution 7-H obtained in Production Example 7-1, titanium oxide (manufactured by Junsei Chemical Co., Ltd .; rutile type, average particle size of 1.5 to 2.1 μm) is converted into titanium atoms. Then, the mixture was added to 0.02 parts by mass per 100 parts by mass of the hydrogenated block copolymer, and sufficiently mixed using a lab solution (manufactured by Primics Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-2. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Example 7-3>
With respect to the hydrogenated block copolymer solution 7-H obtained in Production Example 7-1, titanium hydride (Osaka Titanium Technologies Co., Ltd., particle size: 45 μm) was converted to a hydrogenated block copolymer in terms of titanium atoms. It added so that it might be set to 0.02 mass part per 100 mass parts, and fully mixed using the laboratory solution (made by Primix Co., Ltd.). Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-2. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Examples 7-4, 7-6>
A 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 as shown in Table 2. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Example 7-5>
An equal mass of cyclohexane was added to the block copolymer solution 7 obtained in Production Example 7-B, the hydrogenation catalyst prepared as described above was added, a hydrogenation reaction was performed, and a hydrogenated block copolymer was added. A combined solution 7-5 was obtained. Hydrogenated block copolymer solution 7-5: Water = 1: 2 (mass ratio) was added to the copolymer solution, and the mixture was mixed with Lab Solution (manufactured by Primix Co., Ltd.). After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer. On the other hand, 0.3 part by mass was added and mixed 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. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 7-7>
The hydrogenation catalyst prepared as described above was added to the block copolymer solution 7 obtained in Production Example 7-B, and a hydrogenation reaction was performed to obtain a hydrogenated block copolymer solution 7-7. . When a part of the hydrogenated block copolymer solution 7-7 was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 18 mol%. Met. Hydrogenated block copolymer solution 7-7: Water = 1: 2 (mass ratio) was added in an amount of water to the copolymer solution, and mixed with Lab Solution (manufactured by Primix Co., Ltd.). After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer. On the other hand, 0.3 part by mass was added and mixed well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-7 containing lithium titanate as a titanium compound. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 7-8>
With respect to the hydrogenated block copolymer solution 7-H obtained in Production Example 7-1, titanium oxide (manufactured by Junsei Chemical Co., Ltd .; rutile type, average particle size 1.5 to 2.1 μm) and titanium hydride Labo Solution (Primix Co., Ltd.) was added (Osaka Titanium Technologies Co., Ltd., particle size: 150 μm) to 0.01 parts by mass per 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The mixture was sufficiently mixed. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 7-8. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Examples 8 and 9>
The amount of TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent, and methanol was changed as shown in Table 2, and the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound was changed. A hydrogenated block copolymer composition was obtained in the same manner as in Production Example 6 except that the amount was 40 mol%. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.

<Production Example 10>
A stainless steel autoclave with a stirrer and a jacket with a volume of 40 L was washed, dried, and purged with nitrogen, charged with 5960 g of cyclohexane, and warm water was passed through the jacket to set the content at 65 ° C. TMEDA 5.5 g and n-butyllithium cyclohexane solution (10.04 g pure) were added, and a cyclohexane solution containing styrene (607 g pure) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (2428 g in pure content) 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 cause a coupling reaction. As the coupling agent, Epototo ZX-1059 (Nippon Steel & Sumikin Chemical Co., Ltd.) and cyclohexane mixed at a mass ratio of 90:10 were used. After adding the coupling agent, 3.65 g of methanol was added to inactivate it. When a part of the obtained solution was extracted and analyzed, the obtained block copolymer composition had a styrene content of 20% by mass and an average vinyl bond content of the butadiene part of 35 mol%. Further, the content of the component (A) in the obtained block copolymer is 80% by mass, the weight average molecular weight is 35,000, the content of the component (B) is 20% by mass, and the weight average The molecular weight was 70,000.

  The hydrogenation catalyst prepared as described above was added to the obtained block copolymer composition solution to carry out a hydrogenation reaction. When a part of the hydrogenated block copolymer solution was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 40 mol%. .

  Water in an amount of hydrogenated block copolymer solution: water = 1: 2 (mass ratio) was added to the hydrogenated block copolymer solution and mixed with Lab Solution (manufactured by Primics Co., Ltd.). The copolymer solution was separated by standing. Thereafter, the hydrogenated block copolymer solution was separated by a centrifuge (manufactured by Kubota Corporation), and only the supernatant of the copolymer solution was collected. 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer composition and mixed well. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer composition of Production Example 10. Table 2 shows the result of analyzing a part of the obtained hydrogenated block copolymer.

<Production Example 11>
Polymerization was carried out by the following method using a stirrer having an internal volume of 10 L and a jacketed tank reactor. 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 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 fed to the reactor at a constant rate. At this time, the addition rate was adjusted so that the start of addition and the end of addition of the two types of solutions would be the same. The polymerization conversion of styrene and butadiene was 100%.

  Next, a cyclohexane solution of Epototo ZX-1059 was added, and methanol was added to inactivate it. When a part of the obtained solution was extracted and analyzed, the obtained block copolymer composition had a total content of styrene of 25% by mass, and the content of styrene in a 25-mer or higher was 14% by mass, component (A) and component (B) have random blocks represented by Ar-D / Ar and (Ar-D / Ar) 2X, respectively, and the average vinyl bond content in the butadiene part Was 40 mol%. Further, the content of the component (A) in the obtained block copolymer is 70% by mass, the weight average molecular weight is 90,000, the content of the component (B) is 30% by mass, and the weight average The molecular weight was 180,000.

  The hydrogenation catalyst prepared as described above was added to the obtained block copolymer composition solution to carry out a hydrogenation reaction. When a part of the hydrogenated block copolymer solution was extracted and analyzed, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 50 mol%. .

  The obtained hydrogenated block copolymer solution and water in an amount such that the mass ratio of water was 1: 2 were added to the copolymer solution, and mixed with Lab Solution (manufactured by Primix Co., Ltd.). After standing and separating and separating the copolymer solution, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the hydrogenated block copolymer. On the other hand, 0.3 part by mass was added and mixed 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 with respect to 100 parts by mass of the hydrogenated block copolymer was 0.009 parts by mass, and the amount of titanium having a particle size 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 above-described method for producing an adhesive composition. Furthermore, the adhesive tape was obtained with the preparation method of the adhesive tape mentioned above. Using these adhesive compositions and adhesive tapes, the physical properties of the adhesive compositions described above were measured (evaluation of the adhesive composition, evaluation α of the adhesive tape, evaluation of the quality of the adhesive tape). It was. These results are shown in Table 3.

<Examples 2-7, 9-12, 15-19>
Instead of the hydrogenated block copolymer of Production Example 1, Production Examples 2-6, 7-1, 7-2, 7-3, 7-5, 7-6, 7-7, 7-8, 8, Except that the hydrogenated block copolymer compositions 9 and 11 were used, the same operation as in Example 1 was carried out to produce an adhesive composition and a pressure-sensitive adhesive tape, respectively, and the characteristics were evaluated. These results are shown in Table 3.

<Example 8>
Instead of the hydrogenated block copolymer composition of Production Example 1, the hydrogenated block copolymer composition of Production Example 7-2 was used, and instead of Quinton R100 (manufactured by Nippon Zeon Co., Ltd.), Archon M100 ( Except having used Arakawa Chemical Industries Ltd.), operation similar to Example 1 was performed, the adhesive composition and the adhesive tape were each produced, and the characteristic was evaluated. These results are shown in Table 3.

<Examples 13 to 14>
Instead of the hydrogenated block copolymer composition of Production Example 1, the hydrogenated block copolymer composition of Production Examples 5 and 7-1 was used, and instead of Quinton R100 (manufactured by Nippon Zeon Co., Ltd.), Except having used S100 (made by Idemitsu Kosan Co., Ltd.), operation similar to Example 1 was performed, the adhesive composition and the adhesive tape were each produced, and the characteristic was evaluated. These results are shown in Table 3.

<Examples 20 to 22, Comparative Example 1>
Instead of the hydrogenated block copolymer composition of Production Example 1, the hydrogenated block copolymer composition of Production Example 5-H, Production Example 7-B, Production Example 10, and Production Example 7-4 was used. Except for the above, the same operation as in Example 1 was performed to prepare an adhesive composition and a pressure-sensitive adhesive tape, and the characteristics were evaluated. These results are shown in Table 3.

<Examples 23 to 36>
(A1) Non-hydrogenated styrene-isoprene block copolymer (A1-1) D1161 (manufactured by Kraton Polymer Co., Ltd.)
SI / SIS, styrene content 16% by mass, SI content 20% by mass
(A1-2) Quintac 3520 (manufactured by Nippon Zeon)
SI / SIS, styrene content 15% by mass, SI content 78% by mass
(A2) Hydrogenated styrene-butadiene block copolymer (A2-1) G1726 (manufactured by Kraton Polymer Co., Ltd.)
SEB / SEBS, styrene content 30% by mass, SEB content 70% by mass
(A2-2) G1652 (manufactured by Kraton Polymer Co., Ltd.)
SEBS, styrene content 30% by mass, SEB content 0%
(A2-3) G1657 (manufactured by Kraton Polymer)
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 (Kuraray)
(A3-4) Septon 2277 (manufactured by Kuraray Co., Ltd.)
(A3-5) Septon 4033 (Kuraray)
(B) Tackifier (B1) Quinton R100 (aliphatic petroleum hydrocarbon resin / manufactured by Nippon Zeon)
(B2) Clearon P125 (hydrogenated terpene resin / Yasuhara Chemical Co., Ltd.)
(C) Softener (C1) Diana Process Oil NS90S (Naphthenic oil / Idemitsu Kosan Co., Ltd.)
(D) Antioxidant (D1) Irganox 1010 (manufactured by Ciba Specialty Chemicals)

  Except for blending these components in the proportions shown in Table 4, a hot-melt adhesive composition was obtained by the above-described method for producing an adhesive composition, and further, by the above-described method for producing an adhesive tape. An adhesive tape was obtained. Using these adhesive compositions and adhesive tapes, the physical properties of the adhesive compositions described above were measured (evaluation of adhesive compositions, evaluation of adhesive tapes β, evaluation of the quality of adhesive tapes). It was. These results are shown in Table 4.

  The adhesive tapes obtained in Examples 33 and 34 were cut into 50 mm × 50 mm, adhered to a SUS plate, placed on a SUS plate so that the adhesive layer was exposed to the sun at the window facing south, and allowed to stand. Two weeks later, when the adhesive tape was peeled off, an odor resulting from the deterioration of the adhesive layer was felt. At this time, the odor of the tape of Example 34 was weaker than that of the tape of Example 33.

Ａｒ：ビニル芳香族炭化水素単量体単位を主体とする重合体ブロックを示す。
Ｄ ：共役ジエン単量体単位を主体とする重合体ブロックを示す。

Ar: A polymer block mainly composed of vinyl aromatic hydrocarbon monomer units.
D: A polymer block mainly composed of a conjugated diene monomer unit.

Ａｒ：ビニル芳香族炭化水素単量体単位を主体とする重合体ブロックを示す。
Ｄ ：共役ジエン単量体単位を主体とする重合体ブロックを示す。
Ｘ ：カップリング剤の残基を示す。

Ar: A polymer block mainly composed of vinyl aromatic hydrocarbon monomer units.
D: A polymer block mainly composed of a conjugated diene monomer unit.
X: represents a residue of a coupling agent.

※−：測定未実施

*-: Not measured

  The adhesive composition of the present invention includes various adhesive tapes, adhesive sheets, adhesive films, adhesive labels, pressure sensitive thin plates, pressure sensitive sheets, surface protective sheets, surface protective films, sanitary materials, various lightweight materials. Can be used for back glue for fixing plastic molded articles, back glue for fixing carpets, back glue for fixing tiles, adhesives, etc., especially for adhesive tapes, adhesive sheets, adhesive films, adhesive labels, surfaces It has industrial applicability as an adhesive for protective sheets, surface protective films, and sanitary materials.

Claims (13)

A polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, and a hydrogenated block copolymer having a polymer block mainly composed of conjugated diene monomer units;
A titanium compound,
The content of the titanium compound is 0.000001 to 2 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms.
Hydrogenated block copolymer composition. The total hydrogenation rate of unsaturated double bonds in the conjugated diene monomer unit is 5 mol% or more and less than 90 mol%,
The hydrogenated block copolymer composition according to claim 1.   The hydrogenated block copolymer composition according to claim 1 or 2, wherein the conjugated diene monomer unit includes a butadiene monomer unit.   The hydrogenation according to any one of claims 1 to 3, wherein an average molecular weight of the polymer block mainly composed of the vinyl aromatic hydrocarbon monomer unit is more than 7,500 and not more than 150,000. Block copolymer composition.   Hydrogen as described in any one of Claims 1-4 whose content of the said titanium compound is 0.000001-0.05 mass part with respect to 100 mass parts of hydrogenation block copolymers in conversion of a titanium atom. Added block copolymer composition.   The content of the titanium compound is more than 0.0075 parts by mass and 0.02 parts by mass or less based on 100 parts by mass of the hydrogenated block copolymer in terms of titanium atoms. The hydrogenated block copolymer composition according to item.   The hydrogenated block co-polymerization according to any one of claims 1 to 6, wherein the titanium compound includes at least one selected from the group consisting of titanium oxide, lithium titanate, hydrous titanium oxide, and titanium hydroxide. Combined composition.   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 includes a hydrogenated block copolymer (A) and a hydrogenated block copolymer (B),
The hydrogenated block copolymer (A) has a polymer block mainly composed of the vinyl aromatic hydrocarbon monomer unit and a polymer block mainly composed of the conjugated diene monomer unit. ,
The hydrogenated block copolymer (B) has at least two polymer blocks mainly composed of the vinyl aromatic hydrocarbon monomer unit, and a polymer block mainly composed of the conjugated diene monomer unit; Have
Ratio of weight average molecular weight of the hydrogenated block copolymer (B) to the hydrogenated block copolymer (A) (weight average molecular weight of the hydrogenated block copolymer (B)) / (the hydrogenated block copolymer) The weight average molecular weight of the polymer (A) is 1.3 to 10,
The content of the hydrogenated block copolymer (A) is 20% by mass or more and 90% by mass with respect to 100% by mass in total of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). Mass% or less,
The content of the hydrogenated block copolymer (B) is 10% by mass to 80% with respect to a total of 100% by mass of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). Mass% or less,
The hydrogenated block copolymer composition as described in any one of Claims 1-8. 100 parts by mass of the hydrogenated block copolymer composition according to any one of claims 1 to 9,
20 to 700 parts by weight of a tackifier,
Containing an adhesive composition. Containing an aromatic vinyl elastomer,
The adhesive composition according to claim 10. Containing a conjugated diene-based synthetic rubber,
The adhesive composition according to claim 10 or 11. Contains natural rubber,
The adhesive composition according to any one of claims 10 to 12.