JP6465599B2 - Block copolymer and adhesive composition - Google Patents

Description

  The present invention relates to a block copolymer 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. However, the adhesive composition obtained using these block copolymers has an insufficient balance of holding power, adhesive strength and melt viscosity, and these improvements have been desired.
As an improvement method thereof, for example, Patent Document 1 discloses an adhesive composition composed of a triblock copolymer and a diblock copolymer. Furthermore, Patent Document 2 discloses an adhesive composition comprising a block copolymer obtained by coupling with a specific bifunctional coupling agent (specific dihalogen compound).
Further, Patent Document 3 discloses an adhesive composition comprising a block copolymer 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 holding power, heat resistance, coating properties, and low odor characteristics of the adhesive composition is still insufficient, and in these balances. Is even insufficient.
The present invention has been made in view of the above-described problems of the prior art, and has excellent holding power, heat resistance, coating properties, and low odor characteristics of the adhesive composition. It is an object of the present invention to provide a hydrogenated block copolymer and a hydrogenated block copolymer composition, which are an adhesive composition having an excellent balance.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have obtained a hydrogenated block copolymer having a specific structure, and the hydrogenated block copolymer and tackifier, respectively. The present inventors have found that an adhesive composition containing a predetermined amount can solve the above-described problems of the prior art, and have completed the present invention.

That is, the present invention is as follows.
[ 1 ]
A hydrogenated block copolymer composition comprising component (A) and component (B),
The component (A) contains a polymer block containing 85% by mass or more of vinyl aromatic hydrocarbon monomer units and a polymer block containing 60% by mass or more of conjugated diene monomer units, and has a weight average molecular weight. on 2 Man以5 00000 Ri der Ru hydrogenated block polymer der below,
Component (B) contains at least two polymer blocks containing at least 85% by mass of vinyl aromatic hydrocarbon monomer units and polymer blocks containing at least 60% by mass of conjugated diene monomer units, average molecular weight of 3 Man以on 1 000 000 der Ru hydrogenated block polymer der less is,
A hydrogenated block copolymer composition that satisfies the following requirements (a) to (d).
(A) The ratio of the weight average molecular weight of component (A) to component (B) (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 to 10
(B) The content of vinyl aromatic hydrocarbon monomer units exceeds 50 % by mass and is 95% by mass or less. (C) The vinyl bond amount before hydrogenation is 15 mo with respect to the total content of conjugated diene monomer units.
1% or more and 90 mol% or less (d) The content of component (A) is 20 mass% or more and 90 mass% or less, and the content of component (B) is 10 mass% or more and 80 mass% or less [ 2 ].
The ratio of the squared content of the vinyl aromatic hydrocarbon monomer unit to the vinyl bond content before hydrogenation (the value of squared content of the vinyl aromatic hydrocarbon monomer unit / before hydrogenation) vinyl bond content) is 5 00 or less on 78 or more, a hydrogenated block copolymer composition according to [1].
[ 3 ]
The hydrogenated block copolymer composition according to [1] or [2] , wherein the content of the vinyl aromatic hydrocarbon monomer unit exceeds 60% by mass .
[ 4 ]
The weight average molecular weight of 5 0 10,000 or less on 7 Man以component (A), [1] ~ hydrogenated block copolymer composition according to any one of [3].
[ 5 ]
The weight average molecular weight of 1 000 000 or less on 14 Man以component (B), [1] ~ [4] hydrogenated block copolymer composition according to any one of.
[ 6 ]
Before Symbol derived from the conjugated diene monomer unsaturated double bonds of the total hydrogenation ratio is less than 5 mol% or more 90 mol%, [1] ~ hydrogenated block copolymer composition according to any one of [5] .
[ 7 ]
[100] 100 parts by mass of the hydrogenated block copolymer composition according to any one of [1] to [6] ,
20 to 700 parts by weight of a tackifier,
Containing an adhesive composition.
[ 8 ]
The adhesive composition according to [7] , which contains an aromatic vinyl elastomer.
[ 9 ]
The adhesive composition according to [7] or [8] , comprising a conjugated diene-based synthetic rubber.
[ 10 ]
The adhesive composition according to any one of [7] to [9] , comprising natural rubber.

  According to the present invention, a hydrogenated block copolymer that has a holding power, heat resistance, coating property, low odor characteristics of an adhesive composition, and becomes an adhesive composition excellent in the balance thereof, And an adhesive composition comprising the block copolymer.

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]
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 block mainly composed of at least one conjugated diene monomer unit. (D) is contained, the weight average molecular weight is 2,000 or more and 1,000,000 or less, and the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer is 45% by mass. The amount of vinyl bonds before hydrogenation is 15 mol% or more and 90 mol% or less with respect to the total content of conjugated diene monomer units.

  The weight average molecular weight of the hydrogenated block copolymer is 2,000 or more and 1,000,000 or less, more preferably 10,000 or more, and further preferably 20,000 or more. Further, it is more preferably 300,000 or less, still more preferably 100,000 or less, and even more preferably 60,000 or less.

  When the weight average molecular weight of the hydrogenated block copolymer is 2,000 or more, the holding power is excellent, and when the weight average molecular weight of the hydrogenated block copolymer is 1,000,000 or less, it is excellent. In addition, a block copolymer and an adhesive composition having low melt viscosity characteristics and productivity can be obtained. The weight average molecular weight of the hydrogenated block copolymer can be determined by the method described in the examples.

  The peak molecular weight of the hydrogenated block copolymer is preferably 2,000 or more, more preferably 10,000 or more, and still more preferably 20,000 or more. Moreover, it is preferably 1,000,000 or less, more preferably 300,000 or less, still more preferably 100,000 or less, and even more preferably 60,000 or less.

When the peak molecular weight of the hydrogenated block copolymer is 2,000 or more, the holding power is excellent, and when the peak molecular weight of the hydrogenated block copolymer is 1,000,000 or less, the low molecular weight is excellent. A block copolymer and an adhesive composition having melt viscosity characteristics and productivity can be obtained. Further, from the viewpoint of low viscosity characteristics and productivity, the peak molecular weight of the hydrogenated block copolymer is preferably 20,000 or more and 60,000 or less.
In addition, the peak molecular weight of a hydrogenated block copolymer can be calculated | required by the method described in an Example.

  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 85% by mass or more, preferably It means 90% 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 85% by mass or more, a block copolymer and an adhesive composition excellent in holding power and heat resistance 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, and an integer of 1 to 6 It is preferable that 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 preferred to have a smaller difference in weight average molecular weight, and the vinyl aromatic hydrocarbon monomer unit content contained in each polymer block (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 hydrocarbon monomer unit mass 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.

  The weight average molecular weight of the polymer block (Ar) was determined after oxidative decomposition of the block copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al. J. Polym.Sci.1, 429 (1946), hereinafter often referred to as “osmium tetroxide decomposition method”), and the obtained decomposition product can be determined by measuring by GPC.

  The content of vinyl aromatic hydrocarbon monomer units contained in each polymer block (Ar) and the content of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer are determined as polymer blocks (Ar ) Is not particularly limited, but the content of the vinyl aromatic hydrocarbon monomer unit mass in the hydrogenated block copolymer is divided by the number of polymer blocks (Ar). 7% or less of the value is preferable, 5% or less is more preferable, 3% or less is further preferable, and 1% or less is even more preferable. 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 block copolymer, it can be obtained.

The hydrogenated block copolymer preferably has a structure having at least two polymer blocks mainly composed of vinyl aromatic hydrocarbon monomer units from the viewpoint of holding power. The structure having at least two polymer blocks mainly composed of vinyl aromatic hydrocarbon monomer units is not particularly limited, and examples thereof include, for example, the formulas Ar-D-Ar, (Ar-D) ₂ X, D- Ar-D-Ar, D- Ar-D-Ar-D, D- (-Ar D) 2 X, and the like and mixtures thereof.

  Content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer of this embodiment exceeds 45 mass%, and is 95 mass% or less. Preferably it exceeds 50 mass%, More preferably, it exceeds 60 mass%. Further, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer is preferably 90% by mass or less, more preferably 80% by mass or less.

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 exceeds 45% by mass, a hydrogenated block copolymer having excellent holding power and heat resistance tends to be obtained. Further, 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 adhesive strength and productivity can be obtained. It is in.
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 this embodiment is 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less. It is. Moreover, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 15 mol% or more, Preferably it is 18 mol% or more, More preferably, it is 20 mol% or more. More specifically, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation of the hydrogenated block copolymer is 15 mol% or more and 90 mol% or less, preferably 18 mol% or more and 80 mol% or less, More preferably, it is 20 mol% or more and 70 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 composition after hydrogenation, and specifically described below. It can be measured by the method described in the examples. 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.
The value obtained by squaring the content of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer is divided by the vinyl bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer. The measured value is preferably 78 or more and 500 or less. More preferably, it is 83 or more, More preferably, it is 88 or more. Further, it is more preferably 400 or less, and further preferably 350 or less. The value obtained by squaring the content of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer is divided by the vinyl bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer. If the measured value is 83 or more, characteristics excellent in heat resistance and coating properties tend to be obtained, and if it is 500 or less, characteristics excellent in productivity tend to be obtained.

The value obtained by squaring the content of vinyl aromatic hydrocarbon monomer units in the hydrogenated block copolymer is divided by the vinyl bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer. The obtained value can be controlled by adjusting the content of vinyl aromatic hydrocarbon monomer units and the amount of vinyl bonds when polymerizing the block copolymer.
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.

Moreover, the hydrogenation rate of the unsaturated double bond based on the conjugated diene monomer unit in the hydrogenated block copolymer of this embodiment is more than 0% and 100 mol% or less. Moreover, from a viewpoint of holding power, heat resistance, and a low odor characteristic, 70 mol% or more is preferable, 80 mol% or more is more preferable, 90 mol% or more is further more preferable, and 99 mol% or less is preferable. From the viewpoint of low melt viscosity characteristics, 5 mol% or more is preferable, 10 mol% or more is more preferable, 20 mol% or more is more preferable, less than 90 mol% is preferable, 75 mol% or less is more preferable, and 65 mol% or less is more preferable.
The hydrogenation rate of the conjugated diene monomer unit in the hydrogenated block copolymer can be measured by the method described in the examples.

  In addition, 90% by mass or more of the vinyl aromatic hydrocarbon monomer unit in the polymer block (Ar) of the present embodiment is preferably a 25-mer or more, more preferably 93% by mass or more, 95 mass% or more is further 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 the hydrogenated block copolymer of the present embodiment, 90% by mass or more of the vinyl aromatic hydrocarbon monomer unit is preferably a 25-mer or more, more preferably 93% by mass or more, 95 mass% or more is further 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 hydrogenated block copolymer, the content of the vinyl aromatic hydrocarbon monomer unit, which is 25-mer or more, is in the above range, so that the adhesive block has excellent adhesive performance, and the balance thereof. In addition, 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 that is 25 mer or more is the weight of the polymer block component consisting of the vinyl aromatic monomer unit determined by the osmium tetroxide decomposition method (however, The vinyl aromatic polymer component having an average degree of polymerization of 24 or less is excluded).

[Hydrogenated block copolymer composition]
The hydrogenated block copolymer composition of this embodiment has two different structures of the following component (A) and component (B) from the viewpoint of improving the balance between the adhesive property and the low melt viscosity property.
The ratio of the weight average molecular weight of component (A) to component (B) (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3-10.

  The component (A) comprises 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 a hydrogenated block polymer to be contained and has a weight average molecular weight of 20,000 or more and 500,000 or less.

  The 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 compound monomer unit. And a weight average molecular weight of 30,000 or more and 1,000,000,000,000 or less.

  When a plurality of polymer blocks (Ar) and / or polymer blocks (D) are present in the hydrogenated block copolymer of component (A) and / or component (B), each polymer block (Ar) and / or each polymer block (D) may have the same or different weight average molecular weight, composition and structure, but there are a plurality of polymer blocks (Ar). From the viewpoint of holding power, heat resistance, and productivity, it is preferable that the difference in the weight average molecular weight of the plural polymer blocks (Ar) is smaller, and the vinyl aromatic carbonization contained in each polymer block (Ar). The smaller difference between the content of the hydrogen monomer unit and the value obtained by dividing the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition by the number of polymer blocks (Ar) Is preferred.

  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.

  The weight average molecular weight of the polymer block (Ar) was determined after oxidative decomposition of the block copolymer composition before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, etal.J.Polym.Sci.1,429 (1946), hereinafter often referred to as “osmium tetroxide decomposition method”), and the decomposition product obtained can be determined by measuring by GPC. The vinyl aromatic hydrocarbon monomer unit content contained in each polymer block (Ar) and the content of the vinyl aromatic hydrocarbon monomer unit mass in the hydrogenated block copolymer composition are overlapped. The difference in the value divided by the number of combined blocks (Ar) is not particularly limited, but the content of the vinyl aromatic hydrocarbon monomer unit mass in the hydrogenated block copolymer composition is determined as the polymer block (Ar). ) Is preferably 7% or less, 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 taking into account the structure of the finally obtained block copolymer composition, it is obtained.

  The content of the component (A) and the component (B) in the hydrogenated block copolymer composition is such that the component (A) is 20% by mass or more and 90% by mass or less, and the component (B) is 10% by mass. % To 80% by mass, preferably component (A) is 25% to 85% by mass, and component (B) is 15% to 75% by mass, more preferably. The component (A) is 30% by mass or more and 80% by mass or less, the component (B) is 20% by mass or more and 70% by mass or less, more preferably the component (A) is 40% by mass or more, It is 75 mass% or less, and a component (B) is 25 mass% or more and 60 mass% or less.

A block copolymer composition and an adhesive having excellent balance between low melt viscosity characteristics and adhesive properties when the content of component (A) and component (B) is within the above range. A composition is obtained.
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) (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 or more and 10 or less. Yes, preferably 1.5 or more and 8.0 or less, more preferably 1.8 or more and 5.0 or less. A block copolymer that is excellent in low melt viscosity property, adhesive property, and excellent balance because the ratio of the weight average molecular weight of component (B) to the weight average molecular weight of component (A) is within the above range. Compositions and adhesive compositions are 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.

  Content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition of this embodiment exceeds 45 mass%, and is 95 mass% or less. Preferably it exceeds 50 mass%, More preferably, it exceeds 60 mass%. Further, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is preferably 90% by mass or less, more preferably 80% by mass or less.

A hydrogenated block copolymer composition and an adhesive having excellent adhesive performance and excellent balance due to the content of the vinyl aromatic hydrocarbon monomer unit being in the above range. There is a tendency to obtain a composition. In particular, when the content of the vinyl aromatic hydrocarbon monomer unit exceeds 45% by mass, a hydrogenated block copolymer having excellent holding power and heat resistance tends to be obtained. Further, when the content of the vinyl aromatic hydrocarbon monomer unit is 95% by mass or less, a hydrogenated block copolymer composition and an adhesive composition having excellent productivity tend to be obtained. is there.
Here, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is not the value for each component, but the content of the entire hydrogenated block copolymer composition, that is, It is the average value of the content of each component.

  The vinyl bond content of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer composition of the present embodiment is 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol. % Or less. Moreover, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 15 mol% or more, Preferably it is 18 mol% or more, More preferably, it is 20 mol% or more. More specifically, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation of the hydrogenated block copolymer composition is 15 mol% or more and 90 mol% or less, preferably 18 mol% or more and 80 mol% or less. More preferably, it is 20 mol% or more and 70 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 vinyl bond amount of the conjugated diene monomer unit before hydrogenation is not the value for each component, but the vinyl bond amount as a whole hydrogenated block copolymer composition, that is, the vinyl bond amount of each component. Average value.
The total hydrogenation rate of unsaturated double bonds based on conjugated diene monomer units in the hydrogenated block copolymer composition of the present embodiment is more than 0% and 100 mol% or less. From the viewpoint of holding power and low odor characteristics, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is more preferable. Moreover, from a viewpoint of a low-viscosity characteristic, less than 90 mol% is preferable, 75 mol% or less is more preferable, and 65 mol% or less is further more preferable.

The total hydrogenation rate of unsaturated double bonds based on the conjugated diene monomer unit in the hydrogenated block copolymer composition can be measured by the method described in Examples.
Here, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene monomer unit in the hydrogenated block copolymer composition is not a value for each component, but a hydrogenated block copolymer composition. It is an average value of the vinyl bond amount of the whole product, that is, the vinyl bond amount of each component.

  The value obtained by squaring the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is the vinyl of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer composition. The value divided by the amount of bonds is preferably 78 or more and 500 or less. More preferably, it is 83 or more, More preferably, it is 88 or more. Further, it is more preferably 400 or less, and further preferably 350 or less. The value obtained by squaring the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition is the vinyl of the conjugated diene monomer unit before hydrogenation in the hydrogenated block copolymer composition. When the value divided by the bond amount is 78 or more, characteristics excellent in heat resistance and coating properties tend to be obtained, and when it is 500 or less, characteristics excellent in productivity tend to be obtained.

  In addition, 90% by mass or more of the vinyl aromatic hydrocarbon monomer unit in the polymer block (Ar) of the present embodiment is preferably a 25-mer or more, more preferably 93% by mass or more, 95 mass% or more is further 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. In addition, there is a tendency that an excellent hydrogenated block copolymer composition and an adhesive composition are obtained. In particular, when the content is 90% by mass or more, a hydrogenated block copolymer composition having excellent holding power and heat resistance tends to be obtained. Moreover, it exists in the tendency for the hydrogenated block copolymer composition and adhesive composition which have the outstanding productivity to be obtained by being 100 mass% or less.

Here, in the polymer block (Ar), the content of the vinyl aromatic hydrocarbon monomer unit which is a 25-mer or more is not a value for each component but a hydrogenated block copolymer composition. The total content, that is, the average value of the content of each component.
In the hydrogenated block copolymer of the present embodiment, 90% by mass or more of the vinyl aromatic hydrocarbon monomer unit is preferably a 25-mer or more, more preferably 93% by mass or more, 95 mass% or more is further 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 hydrogenated block copolymer, the content of the vinyl aromatic hydrocarbon monomer unit, which is 25-mer or more, is in the above range, so that the adhesive block has excellent adhesive performance, and the balance thereof. In addition, excellent hydrogenated block copolymer compositions and adhesive compositions 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 composition and adhesive composition which have the outstanding productivity to be obtained by being 100 mass% or less.

  Here, in the hydrogenated block copolymer composition, the content of the vinyl aromatic hydrocarbon monomer unit that is 25 mer or more is not a value for each component but a hydrogenated block copolymer weight. The content of the combined composition as a whole, that is, the average value of the content of each component. In addition, the content of the vinyl aromatic hydrocarbon monomer unit that is 25 mer or more is the weight of the polymer block component consisting of the vinyl aromatic monomer unit determined by the osmium tetroxide decomposition method (however, The vinyl aromatic polymer component having an average degree of polymerization of 24 or less is excluded).

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 block copolymer of component (A) is 20,000 or more and 500,000 or less, preferably 40,000 or more, more preferably 70,000 or more, and further preferably 100. 1,000 or more. Moreover, it is preferably 400,000 or less, more preferably 300,000 or less, and further preferably 175,000 or less. When the weight average molecular weight of the component (A) is 20,000 or more, the productivity is excellent, and when the weight average molecular weight of the component (A) is 500,000 or less, excellent low melt viscosity characteristics are obtained. A hydrogenated block copolymer composition and an adhesive composition are obtained. In particular, from the viewpoint of holding power and productivity, the weight average molecular weight of the block copolymer of component (A) is preferably 70,000 or more and 500,000 or less.
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) 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, m, n and k represent an integer of 1 or more, It is preferably an integer, Ar in the case where a plurality is present may be the same or different from the type of vinyl aromatic hydrocarbon monomer, and D in the case where a plurality is present is the type of conjugated diene monomer or The molecular weight may be the same or different, but the above-described embodiment is preferably used when a plurality of Ar are present.

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

  The weight average molecular weight of the component (B) block copolymer is 30,000 or more and 1,000,000 or less, preferably 100,000 or more, more preferably 140,000 or more, More preferably, it is 200,000 or more. Moreover, it is preferable that it is 900,000 or less, and it is more preferable that it is 800,000 or less.

When the weight average molecular weight of the component (B) is 30,000 or more, it has excellent holding power and adhesive strength, and the weight average molecular weight of the component (B) is 1,000,000 or less. Thus, a hydrogenated block copolymer composition and an adhesive composition having excellent low melt viscosity characteristics can be obtained. In particular, from the viewpoint of holding power, the weight average molecular weight of the component (B) is preferably 100,000 or more and 1,000,000 or less, more preferably 140,000 or more and 1,000,000 or less. preferable. When the low melt viscosity characteristic is particularly important, the weight average molecular weight of the component (B) block copolymer is preferably 180,000 or less, and more preferably 150,000 or less.
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 (xii), 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, Preferably, it is a positive integer of 6 or less. Ar in the case of plural occurrences may be the same or different in the kind of the vinyl aromatic hydrocarbon monomer. The type and molecular weight of the mer may be the same or different, but when a plurality of Ar are present, the above-described embodiment is preferably used.

Component (B) has the formula Ar-D-Ar, (Ar -D) 2 X, D-Ar-D-Ar, D-Ar-D-Ar-D, D- (Ar-D) 2 X, [ D- (Ar-D) ₁ ] _3- X, [(Ar-D) ₁ ] _3- X, [D- (Ar-D) ₁ ] _4- X, and / or [(Ar-D) ₁ ] It is preferable to include a block copolymer represented by _4- X. When component (B) contains such a block copolymer, a hydrogenated block copolymer composition and an adhesive composition that are excellent in productivity and adhesive properties tend to be obtained.
From the viewpoint of holding power and adhesive strength, component (B) is a polymer block mainly composed of two vinyl aromatic hydrocarbon monomer units and a polymer mainly composed of at least one conjugated diene compound monomer unit. It is preferable that it is a hydrogenated block copolymer composition containing a block.

Further, the block copolymer of component (B) has a weight average molecular weight of 140,000 or more, a polymer block mainly composed of two vinyl aromatic hydrocarbon monomer units, and at least one conjugated diene unit. More preferred is a hydrogenated block copolymer composition containing a polymer block mainly composed of a monomer unit. As a hydrogenated block copolymer composition containing a polymer block mainly composed of two vinyl aromatic hydrocarbon monomer units and a polymer block mainly composed of at least one conjugated diene monomer unit, is not particularly limited, for example, the formula Ar-D-Ar, (Ar -D) 2 X, D-Ar-D-Ar, D-Ar-D-Ar-D, D- (Ar-D) 2 X, And a mixture thereof.

[Method for Producing Hydrogenated Block Copolymer and Hydrogenated Block Copolymer Composition]
A hydrogenated block copolymer and a hydrogenated block copolymer composition are prepared by polymerizing at least a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent using an organic lithium compound as a polymerization initiator. Polymerization step for obtaining a polymer, hydrogenation step for hydrogenating double bonds in the conjugated diene monomer unit of the obtained polymer, desolvation for removing the solvent of the solution containing the hydrogenated block copolymer The solvent process can be sequentially performed for production. 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.

  In the case of a hydrogenated block copolymer composition having two different structures, component (A) and component (B), component (A) and component (B) of the composition are prepared separately and mixed later. Or may be manufactured at the same time. 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>
A conjugated diene monomer 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 is not particularly limited. For example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethyl. Examples thereof include styrene and N, N-diethyl-p-aminoethylstyrene. 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.
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.

  In the case of a hydrogenated block copolymer composition comprising a hydrogenated block copolymer having two different structures of component (A) and component (B), component (A) and component (B) in the deactivation step The content of can be controlled by adjusting the molar amount of the quenching agent to the addition amount of the polymerization initiator. 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 a viewpoint of heat-resistant aging property of the block copolymer composition 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 this embodiment that can be produced as described above has a polar group-containing functional group containing an atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin bonded to the block copolymer. A so-called modified polymer 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.

[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. Contains other components described below. Such an adhesive composition of this embodiment has excellent holding power, adhesive strength, heat resistance, low melt viscosity characteristics, coating properties, and low odor characteristics of the adhesive composition. It becomes the adhesive composition which is excellent in the balance.

  In the case of a hydrogenated block copolymer composition comprising a hydrogenated block copolymer having two different structures of component (A) and component (B), depending on the application, in the block copolymer composition It is preferable to select the weight average molecular weights of the components (A) and (B) and adjust the blending amounts of the components such as the tackifier and the softener.

(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, hydrogenated rosin, natural rosin glycerol ester, modified rosin glycerol ester, natural rosin pentaerythritol ester, modified rosin pentaerythritol ester, water Pentaerythritol ester of rosin, natural terpene copolymer, three-dimensional polymer of natural terpene, hydrogenated derivative of hydrogenated terpene copolymer, polyterpene resin, hydrogenated derivative of phenolic modified terpene resin, aliphatic petroleum hydrocarbon resin, fat Examples include hydrogenated derivatives of aromatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins, hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins, etc. can do. These tackifiers can be used alone or in combination of two or more.

As the tackifier, a liquid type tackifier resin can be used as long as the color tone is colorless to light yellow and has substantially no odor and good thermal stability.
20-700 mass parts is preferable, as for content of a tackifier, More preferably, it is 40-500 mass parts, More preferably, it is 60-400 mass parts. When the content of the tackifier is within the above range, the adhesive property is further improved.

  If the composition requires high adhesiveness, change in adhesive strength over time or creep performance (smaller values are better), heat resistance, etc., the block copolymer non-glass phase block (usually Is 20 to 75% by mass of a tackifier resin having an affinity for the intermediate block) and 0.1 to 30% by mass of a tackifier having an affinity for the block (usually the outer block) of the glass phase of the block polymer More preferably.

  As a tackifying resin having an affinity for the glass phase block, a terminal block tackifying resin is preferred. Examples of the tackifying resin include homopolymers or copolymers that are mainly aromatic resins and contain vinyltoluene, styrene, α-methylstyrene, coumarone, or indene. Furthermore, among these, Kristalex, Plastolyn, and Piccotex (trade name, manufactured by Eastman Chemical Co., Ltd.) having α-methylstyrene are preferable. The amount of the end block tackifying resin used in the composition is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 1 to 20% by mass, and still more preferably in the range of 2 to 12% by mass.

  As a composition, a tackifier resin used when high initial adhesive strength, high wettability, low melt viscosity or high coatability of the pressure-sensitive adhesive composition is required is a petroleum resin having an aroma content of 3 to 12% by mass. preferable. The aroma content is more preferably 4 to 10% by mass, and hydrogenated petroleum resin is particularly preferable.

  When the composition requires high initial adhesive strength, high wettability, low melt viscosity or high coatability of the adhesive composition, it is preferable to contain a styrene oligomer. The content of the styrene oligomer is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 8% by mass or less of the adhesive composition. The styrene oligomer is not particularly limited, and examples thereof include Piccolastic A5 (trade name) and Piccolastic A75 (trade name, manufactured by Eastman Chemical Co.).

(Softener)
Although it does not specifically limit as a softening agent, For example, oil, plasticizers, synthetic liquid oligomers, and mixtures thereof, such as well-known paraffin type, naphthenic type, aroma type process oil, and these mixed oils are mentioned.
Although it does not specifically limit as a commercial item of a softening agent, For example, Diana Fresia S32 (brand name) by the Idemitsu Kosan company, Diana process oil PW-90 (brand name), Diana process oil NS-90S (brand 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 Trade name), KN4010 (trade name) manufactured by PetroChina Company, and the like.

  Moreover, it is preferable that content of a softening agent is 0-500 mass parts, More preferably, it is 10-400 mass parts, More preferably, it is 20-300 mass parts. When the content of the softening agent is within the above range, the adhesive property is further improved.

(Other ingredients)
As needed, the adhesive composition of this embodiment is an antioxidant, a block copolymer constituting the adhesive composition of this embodiment, or an aromatic vinyl other than the block copolymer composition. Stabilizers such as elastomers, synthetic rubbers, natural rubbers or polymers, waxes, light stabilizers, and other additives may be included.

  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)] a Hindered phenol antioxidants such as relates; sulfur antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) Examples thereof include phosphorous antioxidants such as phosphite and tris (2,4-di-t-butylphenyl) phosphite.

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 565 (trade name), Irganox HP2225FF (trade name), Irgafos 168 (trade name) and Irganox 1520 (trade name), manufactured by Johoku Chemical Co., Ltd. An example is JF77 (trade name). These stabilizers can be used alone or in combination.
Although content of antioxidant is arbitrary, Preferably it is 5 mass parts or less with respect to 100 mass parts of adhesive compositions.

  In the present specification, “other than the block copolymer or block copolymer composition used in this embodiment” does not correspond to any of the block copolymer or block copolymer composition of this embodiment. Means. Synthetic rubber or polymer other than the block copolymer or block copolymer composition used in the present embodiment is not particularly limited, but for example, polyolefin resin or vinyl aromatic thermoplastic resin, natural rubber, conjugated diene type Examples thereof include rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, polypentenamer rubber, and aromatic vinyl elastomer. Examples of the polyolefin resin include, but are not limited to, atactic polypropylene and ethylene-ethyl acrylate copolymer. Examples of the conjugated diene rubber include, but are not limited to, isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber. Here, the “aromatic vinyl-based elastomer” in the present embodiment does not correspond to any of the block copolymer or the block copolymer composition in the present embodiment. That is, the aromatic vinyl elastomer in the present embodiment is not limited to the following, but for example, a styrene-butadiene block copolymer other than the block copolymer used in the present embodiment, a styrene-isoprene block copolymer. , Hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. As the synthetic rubber or polymer other than the block copolymer or the block copolymer composition used in the present embodiment, the content of the above synthetic rubber or polymer is arbitrary, but preferably 100 mass of the adhesive composition. 0.5 parts by mass or more and 95 parts by mass or less with respect to parts.

If the composition requires reduction of adhesive residue when the composition is peeled off, suppression of changes in adhesive strength over time, or creep properties (smaller values are better), etc., a hydrogenated styrene block copolymer It is preferable to use together. Preferred styrenic block copolymers include S-EB-S, S-EP-S, S-EEP-S (S: polystyrene block, EB: ethylene / butylene copolymer block, EP and EEP: ethylene / propylene. A copolymer block) is preferred. As styrene content of this styrene-type block copolymer, the range of 12 mass%-45 mass% is preferable, The range of 13 mass%-40 mass% is more preferable, The range of 15 mass%-35 mass% is further preferable. In view of high flexibility and compatibility, the S content in the hydrogenated styrene block copolymer is preferably 30% by mass or less, more preferably 21% by mass or less, and further preferably 15% by mass. Furthermore, from the viewpoint of high flexibility and compatibility, the B component in the EB block of S-EB-S is preferably high, preferably 35 mol% or more, preferably 45 mol% or more, preferably 55 mol% or more, 60 mol% or more is most preferable.
It is preferable that the hydrogenation rate of the unsaturated group in the conjugated diene in the styrenic block copolymer exceeds 90 mol%.

  When the composition requires high flexibility, high adhesion, suppression of gelation, high economic efficiency, etc., a block copolymer having non-hydrogenated isoprene or butadiene may be used in combination. More preferred block copolymers include S-I-S, (S-I) nX, S-B-S, (S-B) nX, (S-I-B) nX, S- (I / B ) -S (S: polystyrene block, I: polyisoprene block, B: polybutadiene block, I / B: isoprene / butadiene copolymer block, X: residue of coupling agent). Two or more of these may be used in combination. Among these, (SI) nX and (SB) nX are more preferable. In the case of (SI) nX, the styrene content is preferably 20% by mass or less. In the case of (SB) nX, the styrene content is preferably in the range of 28% by mass to 45% by mass, and more preferably in the range of 34% by mass to 44% by mass. (SI) A structure containing nX and a diblock is more preferred, and the diblock content is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. Moreover, the structure containing (SB) nX and a diblock is further more preferable, 30 mass% or more is preferable, as for the content of a diblock, 50 mass% or more is more preferable, and 65 mass% or more is further more preferable.

  If the composition requires high low-temperature coatability (low viscosity), creep (smaller value is better), high strength or high elongation, etc., use an ionomer in the range of 5% by mass or less. Also good. Preferred ionomers are polymers or copolymers containing carboxylates, sulfonates or phosphonates that are neutralized or partially neutralized by metal ions.

  In the case of reducing the storage stability at high temperature, high elongation or the amount of tackifying resin in the composition (55% by mass or less, further 45% by mass or less) in the composition, α-olefin is added. It is preferable to contain the used copolymer or propylene homopolymer. The melting point (condition: DSC measurement, 5 ° C./min) of these polymers is preferably 110 ° C. or less, more preferably 100 ° C. or less, and further preferably in the range of 60 ° C. to 90 ° C. These polymers may be resins or elastomers. Moreover, the olefin-type elastomer which has a block is more preferable at the point of creep performance (a smaller value is better). The molecular weight distribution of these polymers is preferably in the range of 1-4, more preferably in the range of 1-3. From the viewpoint of processability, it is more preferable to use two or more of these polymers in combination. As molecular weights of the two types of polymers, it is preferable to use at least 30 to 60,000 and 60,000 to 90,000 polymers in combination, and at least 35,000 to 55,000 and 60,000 to 80,000 polymers. It is more preferable to use together. It is preferable to contain a liquid component (oil etc.) in the composition using these, 20 mass% or more is preferable, and, as for content, 25 mass% or more is more preferable.

  The composition may contain a wax if necessary. The amount of wax added in the composition is preferably 20% by mass or less. If a low melt viscosity, especially a low melt viscosity below 140 ° C. is required, at least one selected from paraffin waxes, microcrystalline waxes and Fischer-Tropsch waxes having a melting point of 50 ° C. to 110 ° C. It is preferable to contain 2-10 mass% of waxes. As for content, the range of 5-10 mass% is more preferable. The melting point of the wax is preferably 65 ° C. or higher. 70 degreeC or more is more preferable, and 75 degreeC or more is further more preferable. Moreover, the softening point of the tackifier used together at this time is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. At this time, the G ′ (measurement condition: 25 ° C., 10 rad / s) of the obtained composition is preferably 1 Mpa or less, and more preferably 7 ° C. or less.

  If necessary, the composition may contain a polymer, a tackifier, a wax or the like to which a polar group-containing functional group containing an atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur, tin and the like is bonded. Polymers, tackifiers, waxes, etc., to which polar group-containing functional groups are bonded are not particularly limited, but so-called modified polymers bonded to block copolymers, and block copolymer components as modifiers such as maleic anhydride And a modified block copolymer modified with the above, an oil whose side chain or terminal is modified with an amine, epoxy, carboxylic acid, carboxylic anhydride, or the like, a modified wax obtained by oxidizing polyethylene or modifying maleic anhydride. By using such a composition, it is possible to improve the adhesive property to an adherend having a high SP value such as a resin such as acrylic resin, vinyl chloride, nylon, or a crosslinked product thereof, and glass, metal, etc. it can.

  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; hindered amine light stabilizers and the like.

  The adhesive composition of this embodiment can further contain a fine particle filler as another additive. The fine particle filler is not particularly limited as long as it is generally used. The fine particle filler is not particularly limited, and examples thereof include mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, baked clay, and starch. 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.
When reducing the adhesive residue of the composition, G ′ (measurement condition: 25 ° C., 10 rad / s) of the pressure-sensitive adhesive is preferably 20000 or less, and more preferably 15000 or less. The amount of liquid diluent in the composition is preferably 60% by mass or less. They are particularly useful for dermal application of adhesives, including transdermal drug delivery applications.

[Method for producing adhesive composition]
The adhesive composition of the present embodiment is prepared by mixing the above-described block copolymer composition, a tackifier, a softener, and other additives 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.

[Method of applying adhesive composition]
The method of applying the adhesive is not particularly limited as long as the desired product can be obtained. For example, a method of dissolving the adhesive composition in a solvent and applying the solution or adhesive Examples of the coating method include a hot melt coating method in which the coating 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. Although it does not specifically limit as a contact coating method, For example, slot coater coating, roll coater coating, etc. are mentioned. Further, the non-contact coating method is not particularly limited. For example, spiral coating that can be applied in a spiral shape, omega coating or control seam coating that can be applied in a wave shape, slot spray coating or curtain spray that can be applied in a planar shape, and the like. Examples include coating and dot coating that can be applied in the form of dots.

[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 In particular, it can be suitably used for adhesive tapes, adhesive sheets / films, adhesive labels, surface protective sheets / films, and hygiene adhesives.

  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, peak molecular weight>
The weight average molecular weight and peak molecular weight of the hydrogenated block copolymer crumb are obtained by using a calibration curve (created by using the standard polystyrene peak molecular weight) obtained from the measurement of commercially available standard polystyrene. Based on. When the hydrogenated block copolymer is a hydrogenated block copolymer composition comprising hydrogenated block copolymers having two different structures of component (A) and component (B), the peak having the smallest weight average molecular weight is obtained. The peak having the largest weight average molecular weight next to component (A) and component (A) was determined in the same manner 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 the block copolymer composition is dissolved in chloroform, and an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450) is used to absorb the 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 partially hydrogenated block copolymer was precipitated and recovered. Next, the partially hydrogenated block copolymer was extracted with acetone, and the partially 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

<Contents of (1-4) Component (A) and Component (B)>
When the hydrogenated block copolymer is a hydrogenated block copolymer composition comprising a hydrogenated block copolymer having two different structures of component (A) and component (B), the measurement is performed according to (1-1) above. The ratio of the peak area of the component (A) to the total peak area of the elution curve was taken 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): Measurement of physical properties of adhesive composition]
(Preparation of adhesive composition)
300 parts by mass of Alcon M100 (Arakawa Chemical Industries, Ltd.) as a tackifier and PW-90 (Idemitsu Kosan Co., Ltd.) as a softener, relative to 100 parts by mass of the hydrogenated block copolymer Is mixed with 100 parts by mass and heated and mixed using an oil bath, and melt-kneaded at 180 ° C. for 60 minutes by a mixer (model: L5M-A, Silverson Nippon Co., Ltd., paddle type 4 blades), A hot-melt adhesive composition was obtained.
In the adhesive composition, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) is used as a stabilizer with respect to 100 parts by mass of the block copolymer composition. ) -4-Methylphenyl acrylate was blended by 1 part by mass.

<(2-1) Coatability of adhesive composition>
Spiral coating of the adhesive composition was performed using a hot melt dispenser (DP-300P manufactured by Suntool Co., Ltd.). The coating temperature was 150 ° C., the discharge pressure was 0.1 MPa, the nozzle diameter was 1.0 mmφ, and the coating speed was 30 m / min. The coatability was evaluated according to the following criteria. Evaluation shall be (circle), (triangle | delta), x from a favorable order.

When a spiral pattern can be obtained and the wire diameter is constant: ○
When a spiral pattern can be obtained, but the wire diameter is not constant:
When spiral pattern cannot be obtained: ×

<(2-2) Melt viscosity of adhesive composition>
The temperature was measured at 140 ° C. using a Brookfield viscometer (DV-III manufactured by Brookfield). Based on the obtained value, the melt viscosity was evaluated according to the following criteria. Evaluation is ◎, ○, △, × from the good order.
Melt viscosity (140 ° C.) (mPa · s) ≦ 2500: ◎
2500 <melt viscosity (140 ° C.) (mPa · s) ≦ 3500: ○ 3500 <melt viscosity (140 ° C.) (mPa · s) ≦ 6000: Δ
6000 <melt viscosity (140 ° C.) (mPa · s): ×

<(2-3) Evaluation of low odor characteristics of adhesive composition>
The low odor characteristic of the adhesive composition was evaluated by a sensory test. Ten minutes after the specific amount of the adhesive composition was put in a 20 cm × 8 cm PE bag and sealed, the smell in the bag was smelled, and the smell was smelled. Based on the obtained results, the low odor characteristics were evaluated according to the following criteria. Evaluation shall be (circle), (triangle | delta), x from a favorable order.
When the adhesive composition does not feel odor even when the adhesive composition is 10 g or more: ○ When the adhesive composition does not feel odor when the adhesive composition is 5 g or more and less than 10 g: Δ
When the adhesive composition is less than 5 g and feels odor: ×

(Production of adhesive tape)
The melted adhesive composition was cooled to room temperature and dissolved in toluene. The obtained toluene solution is coated on 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 toluene and produce an adhesive tape with an adhesive layer thickness of 40 μm. did.

<(2-4) Adhesive strength of adhesive composition>
A 25 mm wide adhesive tape was attached to the SUS plate and peeled off at a peeling speed of 300 mm / min, and the 180 ° peeling force at that time was measured. Based on the obtained peeling force, the adhesive strength of the adhesive composition was evaluated according to the following criteria. The evaluation is ◎, ○, Δ, × from the best order.
20 ≦ Adhesive strength (N / 10 mm): ◎
14 ≦ Adhesive strength (N / 10 mm) <20: ○
8 ≦ Adhesive strength (N / 10 mm) <14: Δ
Adhesive strength (N / 10 mm) <8: ×

<(2-5) Holding power of adhesive composition>
Adhesive tape was applied so that an area of 25 mm × 25 mm was in contact with the SUS plate, and a load of 1 kg was applied at 40 ° 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. The evaluation is ◎, ○, Δ, × from the best order.
4000 ≦ retention force (40 ° C.) (minutes): ◎
1000 ≦ holding force (40 ° C.) (min) <4000: ○ 300 ≦ holding force (40 ° C.) (min) <1000: Δ
Holding power (40 ° C.) (minutes) <300: ×

<(2-6) Heat resistance of adhesive composition>
Adhesive tape was applied so that an area of 25 mm × 25 mm was in contact with the SUS plate, and a load of 1 kg was applied at 60 ° 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. The evaluation is ◎, ○, Δ, × from the best order.
100 ≦ holding force (minutes): ◎
50 ≦ holding force (min) <100: ○ 20 ≦ holding force (min) <50: Δ
Holding power (minutes) <20: ×

[(3): Preparation of hydrogenation catalyst]
In Examples and Comparative Examples described later, a hydrogenation catalyst used for preparing a hydrogenated block copolymer or a composition thereof 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.

[(4): Preparation of hydrogenated block copolymer and hydrogenated block copolymer composition]
<Production Example 1-B, Production Example 1-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. 1.2 g of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) and n-butyllithium cyclohexane solution (5.74 g in pure content) were added, and a cyclohexane solution containing styrene (purified content) 710 g) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (1670 g in pure content) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Subsequently, a cyclohexane solution containing styrene (710 g in pure content) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. After polymerization of styrene, 2.40 g of methanol was added to inactivate it. When the obtained solution was analyzed, the obtained block copolymer composition had a styrene content of 46% by mass and an average vinyl bond content of the butadiene portion of 23% by mass. Moreover, the weight average molecular weight was 56,000. A part of the obtained block copolymer solution was extracted, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added in an amount of 0. 0 to 100 parts by mass of the block copolymer. 3 parts by mass was added and mixed well. Thereafter, the solvent was removed by heating to obtain a block copolymer of Production Example 1-B.

  The hydrogenation catalyst prepared as described above was added to the remaining block copolymer solution at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was performed. When the obtained 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 was 35 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. Thereafter, the solvent was removed by heating to obtain a hydrogenated block copolymer of Production Example 1-H.

<Production Examples 2-7>
In the same manner as in Production Example 1-H except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent, and methanol were changed as shown in Table 1, respectively, A polymer was obtained. Table 1 shows the results of analyzing a part of the obtained hydrogenated block copolymer. In addition, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer of Production Examples 1 to 7 which is 25-mer or more obtained by the osmium tetroxide decomposition method is 95% by mass. It was confirmed that this is the case.

<Production Example 8>
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 (3.7 g) and n-butyllithium cyclohexane solution (3.99 g in pure content) were added, and a cyclohexane solution containing styrene (1970 g in pure content) was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 1,3-butadiene (1160 g in pure content) was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 3.44 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, 0.99 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 63% by mass and an average vinyl bond content of the butadiene part of 50% by mass. . In addition, the content of the component (A) in the obtained block copolymer is 65% by mass, the weight average molecular weight is 80,000, the content of the component (B) is 35% by mass, and the weight average The molecular weight was 160,000.

  A hydrogenation catalyst prepared as described above was added to the obtained block copolymer composition solution at 100 ppm based on Ti per 100 parts by mass of the block copolymer, and a hydrogenation reaction was performed. When the obtained 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%. 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 8.

<Production Examples 9 to 11>
Hydrogenated block copolymer in the same manner as in Production Example 8 except that the amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, coupling agent, and methanol were changed as shown in Table 2, respectively. A composition was obtained. Table 2 shows the results of analyzing the obtained hydrogenated block copolymer composition.
In addition, the content of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer composition of Production Examples 8 to 11 which is 25-mer or more obtained by the osmium tetroxide decomposition method is 95. It was confirmed that it was at least mass%.

< Reference Example 1>
Using the hydrogenated block copolymer of Production Example 1-H, 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. These results are shown in Table 3.

< Reference Examples 2-6, Comparative Examples 1-2>
Instead of the hydrogenated block copolymer of Production Example 1, the same operations as in Reference Example 1 except that the hydrogenated block copolymer and the block copolymer of Production Examples 2 to 7 and Production Example 1-B were used. The adhesive composition and the pressure-sensitive adhesive tape were produced, and the characteristics were evaluated. These results are shown in Table 3.

< Reference Example 7>
Instead of the hydrogenated block copolymer of Production Example 1, using the hydrogenated block copolymer of Preparation Example 6, except that further PiccolasticA5 (manufactured by Eastman Chemical Co.) with 20 parts by weight as in Reference Example 1 The adhesive composition and the pressure-sensitive adhesive tape were respectively prepared and the characteristics were evaluated. These results are shown in Table 3.

< Reference Example 8>
Instead of the hydrogenated block copolymer of Production Example 1, using the hydrogenated block copolymer of Preparation Example 6, except that further Plastolyn290 (manufactured by Eastman Chemical Co.) were used 35 parts by weight as in Reference Example 1 The adhesive composition and the pressure-sensitive adhesive tape were respectively prepared and the characteristics were evaluated. These results are shown in Table 3.

<Examples 9 to 11 and Comparative Example 3>
The same procedure as in Reference Example 1 was performed except that the hydrogenated block copolymer compositions of Production Examples 8 to 11 were used instead of the hydrogenated block copolymer of Production Example 1, and an adhesive composition was obtained. And the adhesive tape was produced, respectively, and the characteristic was evaluated. These results are shown in Table 4.

  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 (10)

A hydrogenated block copolymer composition comprising component (A) and component (B),
The component (A) contains a polymer block containing 85% by mass or more of vinyl aromatic hydrocarbon monomer units and a polymer block containing 60% by mass or more of conjugated diene monomer units, and has a weight average molecular weight. on 2 Man以5 00000 Ri der Ru hydrogenated block polymer der below,
Component (B) contains at least two polymer blocks containing at least 85% by mass of vinyl aromatic hydrocarbon monomer units and polymer blocks containing at least 60% by mass of conjugated diene monomer units, average molecular weight of 3 Man以on 1 000 000 der Ru hydrogenated block polymer der less is,
A hydrogenated block copolymer composition that satisfies the following requirements (a) to (d).
(A) The ratio of the weight average molecular weight of component (A) to component (B) (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1.3 to 10
(B) The content of vinyl aromatic hydrocarbon monomer units exceeds 50 % by mass and is 95% by mass or less. (C) The vinyl bond amount before hydrogenation is 15 mo with respect to the total content of conjugated diene monomer units.
1% or more, 90 mol% or less (d) The content of component (A) is 20 mass% or more and 90 mass% or less, and the content of component (B) is 10 mass% or more and 80 mass% or less. The ratio of the squared content of the vinyl aromatic hydrocarbon monomer unit to the vinyl bond content before hydrogenation (the value of squared content of the vinyl aromatic hydrocarbon monomer unit / before hydrogenation) vinyl bond content) is 5 00 or less on 78 or more,
The hydrogenated block copolymer composition according to claim 1 . The hydrogenated block copolymer composition according to claim 1 or 2 , wherein a content of the vinyl aromatic hydrocarbon monomer unit exceeds 60% by mass . Weight average molecular weight of 5 0 10,000 or less on 7 Man以of said components (A),
The hydrogenated block copolymer composition according to any one of claims 1 to 3 . The weight average molecular weight of the component (B) is 1 000 000 or less on 14 Man以,
The hydrogenated block copolymer composition according to any one of claims 1 to 4 . Before Symbol derived from the conjugated diene monomer unsaturated double bonds of the total hydrogenation ratio is less than 5 mol% or more 90 mol%,
The hydrogenated block copolymer composition according to any one of claims 1 to 5 . A hydrogenated block copolymer composition 100 parts by weight of any one of 請 Motomeko 1-6,
20 to 700 parts by weight of a tackifier,
Containing an adhesive composition. The adhesive composition according to claim 7 , comprising an aromatic vinyl-based elastomer. Containing a conjugated diene-based synthetic rubber,
The adhesive composition according to claim 7 or 8 . Contains natural rubber,
The adhesive composition according to any one of claims 7 to 9 .