JP6367648B2 - Self-adhesive adhesive composition and self-adhesive adhesive tape using the same - Google Patents

Description

  The present invention relates to a self-adhesive pressure-sensitive adhesive composition and a self-adhesive pressure-sensitive adhesive tape using the same.

In recent years, vinyl aromatic monomer-conjugated diene monomer block copolymers have been widely used as pressure-sensitive adhesives for self-adhesive tapes from the viewpoints of energy saving, resource saving, and reduction of environmental burden.
In Patent Document 1, two types of polymers having different vinyl aromatic content ratios are blended in a specific ratio, and a self-adhesion force is maintained by adding a filler and a tackifying resin, and an adhesion force to an adherend. An adhesive composition with a limited amount is disclosed.
Patent Document 2 discloses that a self-adhesion force is maintained by adding a vulcanized rubber and a tackifier resin to a styrene-isoprene-styrene block copolymer polymer, and that the adhesive force to the adherend is limited. A composition is disclosed.
Patent Document 3 discloses an adhesive composition in which a tackifying resin is added to a fully hydrogenated polymer, the self-adhesion strength is maintained, and the adhesion strength to an adherend is limited.

JP 2014-1312 A JP 58-57479 A Japanese Patent Laid-Open No. 1-138280

However, even in the above-described conventionally proposed techniques, the effect of improving low adhesive strength, self-adhesion, self-adhesion retention, weather resistance, heat resistance, low odor characteristics, and low-temperature characteristics is still insufficient. These balances are still insufficient.
The present invention has been made in view of the above-described problems of the prior art, and has low adhesive strength, excellent self-adhesion, self-adhesion retention, weather resistance, low odor characteristics, low temperature characteristics, and An object of the present invention is to provide a self-adhesive pressure-sensitive adhesive composition excellent in balance and a self-adhesive tape using the same.

  As a result of intensive studies in order to solve the problems of the prior art, the present inventors have obtained a composition containing a partially hydrogenated block copolymer having a specific structure and a filler. The present inventors have found that the problem can be solved and have completed the present invention.

That is, the present invention is as follows.
[1] following component (a), a self-adhesive tape composition comprising a component (b), and component (c),
(A) 100 parts by mass of partially hydrogenated block copolymer (b) 1 to 300 parts by mass of filler
(C) 4 to 200 parts by mass of tackifying resin The (a) partially hydrogenated block copolymer comprises a polymer block Ar mainly composed of vinyl aromatic hydrocarbon compound units and a conjugated diene compound unit. Having a polymer block D as a main component,
Unsaturated double bond hydrogenation ratio derived from the conjugated diene compound unit is Ri 10～90Mol% der,
The weight average molecular weight is 20,000 or more and 1,000,000 or less,
The content of the vinyl aromatic hydrocarbon block polymer is 10 to 50% by mass,
Before hydrogenation, the vinyl bond amount of the conjugated diene compound unit is 10 to 80 mol%, the cis and trans bond content of the conjugated diene compound unit is 20 to 90 mol%,
It contains component (A) and component (B) which are partially hydrogenated block copolymers having two different structures, and (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1. .3～10 der Ru, self-adhesive tape composition.
[ 2 ] The composition for self-adhesive adhesive tapes according to [1], wherein (b) is a filler containing calcium.
[ 3 ] In the partially hydrogenated block copolymer (a), the content of the vinyl aromatic hydrocarbon compound unit is 10 to 20% by mass, and cis and trans bonds in the conjugated diene compound unit before hydrogenation are present. The composition for self-adhesive pressure-sensitive adhesive tapes according to [1] or [2] , which is hydrogenated in the range of 5 to 25 mol%.
[ 4 ] A self-adhesive adhesive tape in which the composition according to any one of [1] to [ 3 ] is applied to one surface of a substrate.

  According to the present invention, a self-adhesive pressure-sensitive adhesive composition and a self-adhesive composition having low adhesive strength, excellent self-adhesive strength, self-adhesion retention, weather resistance, low odor characteristics, and low-temperature characteristics, and excellent balance between them. An adhesive tape can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.
In the following, the structural unit constituting the polymer is referred to as “˜compound unit”, and when describing as a polymer material, “unit” is omitted, and “˜compound” is simply described.

[(A) Partially hydrogenated block copolymer]
The partially hydrogenated block copolymer contains a polymer block Ar mainly composed of at least one vinyl aromatic hydrocarbon compound unit and a polymer block D mainly composed of at least one conjugated diene compound unit.
The hydrogenation rate of the conjugated diene compound monomer unit (unsaturated double bond based on the conjugated diene compound) contained in the block copolymer is 10 mol% or more and 90 mol% or less.
The weight average molecular weight of the partially hydrogenated block copolymer is preferably 20,000 or more and 1,000,000 or less, more preferably 50,000 or more, and further preferably 70,000 or more. Further, it is more preferably 500,000 or less, further preferably 300,000 or less, and even more preferably 270,000 or less.

When the weight average molecular weight of the partially hydrogenated block copolymer is 20,000 or more, the self-adhesion retention and productivity are excellent, and the weight average molecular weight of the partially hydrogenated block copolymer is 1,000,000. By being the following, the partially hydrogenated block copolymer and the composition for self-adhesive tapes which have the outstanding self-adhesion power are obtained. The weight average molecular weight of the partially hydrogenated block copolymer can be determined by the method described in the examples.
In the present specification, “based mainly on a vinyl aromatic hydrocarbon compound unit” means that the content of the vinyl aromatic hydrocarbon compound unit in the vinyl aromatic hydrocarbon polymer block is 60% by mass or more, preferably Means 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

  Further, in the present specification, “consisting mainly of a conjugated diene compound unit” means that the content of the conjugated diene compound unit in the conjugated diene polymer block is 60% by mass or more, preferably 80% by mass or more. More preferably, it is 90% by mass or more, and more preferably 95% by mass or more. In the present specification, the conjugated diene compound unit is referred to as a conjugated diene compound unit even after hydrogenation.

The structure of the partially hydrogenated block copolymer is not particularly limited, and examples thereof include the following formulas (i) to (vi).
(Ar-D) _n (i)
D- (Ar-D) _n (ii)
Ar- (D-Ar) _n (iii)
Ar- (D-Ar) _n -X (iv)
[(Ar−D) _k ] _m −X (v)
[(Ar-D) _k- Ar] _m- X (vi)
(In the above formulas (i) to (vi), Ar represents a polymer block Ar mainly composed of vinyl aromatic hydrocarbon compound units, D represents a polymer block D mainly composed of conjugated diene compound units, and 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, preferably an integer of 1 to 6, When present, Ar may be the same or different in the type and composition, weight average molecular weight, and structure of the vinyl aromatic hydrocarbon compound, and in the case where a plurality of Ar are present, D represents the type, composition, and weight average of the conjugated diene compound. The molecular weight and structure may be the same or different.)

  The content of the vinyl aromatic hydrocarbon block polymer in the partially hydrogenated block copolymer of the present embodiment is preferably 10% by mass or more, more preferably 11% by mass or more, and further preferably 12% by mass. % Or more. Further, the content of the vinyl aromatic hydrocarbon block polymer in the partially hydrogenated block copolymer is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less. And more preferably 20% by mass or less. When the content of the vinyl aromatic hydrocarbon block polymer in the partially hydrogenated block copolymer used in the present embodiment is in the above range, it has excellent self-adhesion strength and self-adhesion retention, and the balance thereof. In addition, an excellent partially hydrogenated block copolymer and a self-adhesive tape composition tend to be obtained. In particular, when the content of the vinyl aromatic hydrocarbon block polymer is 10% by mass or more, a partially hydrogenated block copolymer and a composition for self-adhesive tape having excellent self-adhesion retention are obtained. It is in. Further, when the content of the vinyl aromatic hydrocarbon block polymer is 50% by mass or less, a partially hydrogenated block copolymer and a composition for self-adhesive tape having an excellent self-adhesive force tend to be obtained. .

  Here, when the partially hydrogenated block copolymer is composed of a plurality of components, the content of the vinyl aromatic hydrocarbon compound unit in the partially hydrogenated block copolymer is not a value for each component but partially hydrogenated. The content of the block copolymer composition as a whole, that is, the average value of the content of each component. The content of the vinyl aromatic hydrocarbon compound unit in the partially hydrogenated block copolymer can be measured by the method described in Examples described later.

  Further, the vinyl bond amount of the conjugated diene compound unit before hydrogenation in the partially hydrogenated block copolymer used in this embodiment is preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably. It is 60 mol% or less, More preferably, it is 50 mol% or less. Further, the vinyl bond amount of the conjugated diene compound unit before hydrogenation is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. When the vinyl bond amount of the conjugated diene compound unit is within the above range, characteristics excellent in productivity, self-adhesion, and self-adhesion retention tend to be obtained.

  Further, the content of cis and trans bonds of the conjugated diene compound unit before hydrogenation in the partially hydrogenated block copolymer used in the present embodiment is preferably 90 mol% or less, more preferably 80 mol% or less, More preferably, it is 75 mol% or less. The content of cis and trans bonds in the conjugated diene compound unit before hydrogenation is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and even more preferably It is 50 mol% or more. When the content of the cis and trans bonds of the conjugated diene compound unit is within the above range, characteristics excellent in productivity, self-adhesion and self-adhesion retention tend to be obtained.

  Here, when the partially hydrogenated block copolymer is composed of a plurality of components, the vinyl bond amount or cis / trans bond content of the conjugated diene compound unit before hydrogenation is not a value for each component but partial hydrogen. This is the vinyl bond content or cis and trans bond content of the added block copolymer as a whole, that is, the average value of the vinyl bond content or cis and trans bond content of each component.

  Further, the vinyl bond amount refers to 1, 1 with respect to the total mol amount of conjugated diene compound units incorporated in the 1,2-bond, 3,4-bond and 1,4-bond bond modes before hydrogenation. It is the ratio of the total mol amount of the conjugated diene compound unit incorporated by 2-bond and 3,4-bond. The content of cis and trans bonds refers to the total mol amount of conjugated diene compound units incorporated in the 1,2-bond, 3,4-bond and 1,4-bond bond modes before hydrogenation. It is the ratio of the total mol amount of the conjugated diene compound unit incorporated in the 1,4-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 1,2-bond without hydrogen addition, 1,1 after hydrogenation, with respect to the total molar amount of conjugated diene compound units incorporated in the 1,4-bond and hydrogenation 1,4-bond bonding mode of The ratio of the total mol amount of the conjugated diene compound unit incorporated in the 2-bond, the 3,4-bond not added with hydrogen and the 3,4-bond after hydrogenation is the vinyl of the conjugated diene compound unit before hydrogenation. Equal to the amount of binding. Therefore, the vinyl bond amount of the conjugated diene compound unit before hydrogenation can be measured by nuclear magnetic resonance spectrum analysis (NMR) using the partially hydrogenated block copolymer composition after hydrogenation, and will be described in detail later. It can be measured by the method described in the examples. In addition, since the value of the content of a vinyl aromatic hydrocarbon compound unit and the value of a weight average molecular weight become the same value before and after hydrogenation, the value after hydrogenation is employ | adopted.

In the hydrogenation step, the conjugated bond of the vinyl aromatic hydrocarbon compound unit may be hydrogenated, but from the viewpoint of self-adhesion and self-adhesion retention, the hydrogenation rate of the conjugated bond of all vinyl aromatic hydrocarbon compound units Is preferably 30 mol% or less, preferably 10 mol% or less, and more preferably 3 mol% or less.
The hydrogenation rate of the conjugated diene compound unit in the partially hydrogenated block copolymer used in the present embodiment is 10 mol% or more and 90 mol% or less, preferably 15 mol% or more, more preferably 20 mol% or more. More preferably, it is 25 mol% or more. With such a hydrogenation rate, the self-adhesion and self-adhesion retention tend to be excellent. Moreover, 80 mol% or less is preferable, as for the hydrogenation rate of a conjugated diene compound unit, 70 mol% or less is more preferable, and 60 mol% or less is further more preferable.

When the hydrogenation rate of the conjugated diene compound unit is within the above range, the partially hydrogenated block copolymer and the self-adhesion have excellent low-temperature characteristics, weather resistance, heat resistance, and excellent balance of self-adhesion and self-adhesion retention. There exists a tendency for the agent composition for adhesive tapes to be obtained.
In the present embodiment, from the viewpoint of weather resistance and low odor characteristics, it is preferable that 80 mol% or more of the amount of vinyl bonds in the conjugated diene compound unit in the partially hydrogenated block copolymer is hydrogenated. 85 mol% or more is more preferable, and 90 mol% or more is more preferable.

  In the present embodiment, from the viewpoints of self-adhesion and self-adhesion retention, 5 to 25 mol% of the content of cis and trans bonds in the conjugated diene compound unit in the partially hydrogenated block copolymer is hydrogenated. It is preferable. 8 mol% or more is more preferable, and 10 mol% or more is further more preferable. 23 mol% or less is more preferable, and 20 mol% or less is still more preferable.

From the viewpoint of the balance of self-adhesion, self-adhesion retention, adhesive strength, and weather resistance, among the conjugated diene compound units of the partially hydrogenated block copolymer, when hydrogenated cis and trans bonds are 5 to 25 mol% More preferably, the content of the vinyl aromatic hydrocarbon compound unit is 10 to 20% by mass.
The hydrogenation rate in the vinyl bond amount and the hydrogenation rate in the cis and trans bonds can be controlled by controlling the vinyl bond amount and the hydrogenation rate in the conjugated diene compound unit.

The hydrogenation rate of the conjugated diene compound unit in the partially hydrogenated block copolymer and the proportion of the conjugated diene compound unit in which cis and trans bonds are hydrogenated can be measured by the method described in Examples.
Here, when the partially hydrogenated block copolymer is composed of a plurality of components, the hydrogenation rate of the conjugated diene compound unit is not a value for each component, but the conjugated diene compound unit as a whole of the partially hydrogenated block copolymer. Is the average value of the hydrogenation rate of the conjugated diene compound unit of each component.

[Block copolymer composition]
The partially hydrogenated block copolymer of this embodiment is a partially hydrogenated block copolymer having two different structures of the following component (A) and component (B) from the viewpoint of improving the balance between self-adhesion and self-adhesion retention. A partially hydrogenated block copolymer composition comprising: At this time, 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 preferably 1.3 to 10. .

The component (A) is a partially hydrogenated block polymer containing a polymer block Ar mainly composed of at least one vinyl aromatic hydrocarbon compound unit and a polymer block D mainly composed of at least one conjugated diene compound unit. And the weight average molecular weight is preferably 20,000 or more and 500,000 or less,
The partially hydrogenated block polymer in which the component (B) contains a polymer block Ar mainly composed of at least two vinyl aromatic hydrocarbon compound units and a polymer block D mainly composed of at least one conjugated diene compound unit. The weight average molecular weight is preferably 30,000 or more and 1,000,000,000,000 or less.

When a plurality of polymer blocks Ar and / or D are present in the partially hydrogenated block copolymer of component (A) and / or component (B), the weight average of each polymer block Ar and D The molecular weight, composition, and structure may be the same or different.
The content of component (A) and component (B) in the partially hydrogenated block copolymer composition is preferably such that component (A) is 20% by mass or more and 90% by mass or less, and component (B ) Is 10% by mass or more and 80% by mass or less, more preferably component (A) is 30% by mass or more and 85% by mass or less, and component (B) is 15% by mass or more and 70% by mass or less. More preferably, the component (A) is 35% by mass or more and 80% by mass or less, and the component (B) is 20% by mass or more and 65% by mass or less, and still more preferably the component (A). Is 40 mass% or more and 75 mass% or less, and a component (B) is 25 mass% or more and 60 mass% or less.

When the content of component (A) and component (B) is within the above range, both the self-adhesion and self-adhesion retention properties are excellent, and the well-balanced partially hydrogenated block copolymer and self-adhesive tape 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. Preferably, it is 1.5 or more and 8.0 or less, more preferably 1.8 or more and 5.0 or less. The ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) is within the above range, so that the self-adhesion force and the self-adhesion retention are excellent, and the partially hydrogenated block co-polymer with excellent balance A combined and self-adhesive tape composition is 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, the ratio of the weight average molecular weight of a component (A) and a component (B) and the ratio of a weight average molecular weight can be measured by the method described in the Example mentioned later. Hereinafter, each component will be described in more detail.

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

The weight average molecular weight of the component (A) block copolymer is preferably 20,000 or more and 500,000 or less, more preferably 30,000 or more, and further preferably 40,000 or more, Even more preferably, it is 70,000 or more. Further, it is more preferably 175,000 or less, still more preferably 150,000 or less, and even more preferably 120,000 or less.
A part having excellent self-adhesiveness when the weight average molecular weight of the component (A) is 20,000 or more and excellent in productivity, and the weight average molecular weight of the component (A) is 500,000 or less. A hydrogenated block copolymer composition and a self-adhesive tape composition are obtained. In addition, the weight average molecular weight of a component (A) can be calculated | required by the method described in an Example.

Although it does not specifically limit as a structure of a component (A), For example, following formula (i)-(vi) is mentioned.
(Ar-D) _n (i)
D- (Ar-D) _n (ii)
Ar- (D-Ar) _n (iii)
Ar- (D-Ar) _n -X (iv)
[(Ar−D) _k ] _m −X (v)
[(Ar-D) _k- Ar] _m- X (vi)
(In the above formulas (i) to (vi), Ar represents a polymer block Ar mainly composed of vinyl aromatic hydrocarbon compound units, D represents a polymer block D mainly composed of conjugated diene compound units, and 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, preferably an integer of 1 to 6, When present, Ar may be the same or different in the type, composition, molecular weight, and structure of the vinyl aromatic hydrocarbon compound. When present in plural, D represents the type, composition, molecular weight, and structure of the conjugated diene compound. It can be the same or different.)

  Among the formulas (i) to (vi), partial hydrogenated block copolymers represented by Ar-D and D-Ar-D are more preferable. Since the component (A) has such a structure, the partially hydrogenated block copolymer composition and the self-adhesive tape have excellent low melt viscosity characteristics, adhesive strength, and tack, and are well balanced. Tend to be obtained.

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

  The weight average molecular weight of the partially hydrogenated block copolymer of the component (B) is preferably 30,000 or more and 1,000,000 or less, more preferably 50,000 or more, and 70,000 or more. More preferably. Further, it is more preferably 500,000 or less, further preferably 400,000 or less, and even more preferably 300,000 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. A partially hydrogenated block copolymer composition and a self-adhesive tape composition having excellent low melt viscosity characteristics can be obtained. In addition, the weight average molecular weight of a component (B) can be calculated | required by the method described in an Example.

From the viewpoint of self-adhesion and self-adhesion retention, component (B) contains a polymer block mainly composed of two vinyl aromatic hydrocarbon units and a polymer block mainly composed of at least one conjugated diene compound unit. It is preferably a hydrogenated block copolymer composition.
Further, the partially hydrogenated 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 units, and at least one conjugated diene compound A partially hydrogenated block copolymer composition containing a polymer block mainly composed of units is more preferable. The partially hydrogenated block copolymer composition containing a polymer block mainly composed of two vinyl aromatic hydrocarbon units and a polymer block mainly composed of at least one conjugated diene compound 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 mixtures thereof Etc.

  The maximum value of the loss coefficient (tan δ) from −100 ° C. to 0 ° C. in the dynamic viscoelastic spectrum of the hydrogenated block copolymer composition comprising the component (A) and the component (B) is 0.4 to It is preferably 4.0. When the maximum value of the loss factor is 0.4 or more, a block copolymer and an adhesive composition having excellent texture and tack are obtained, and when the loss coefficient is 4.0 or less, the block copolymer having excellent holding power is obtained. A polymer and an adhesive composition are obtained. From the same viewpoint, 0.5 or more is more preferable, 0.7 or more is more preferable, 0.8 or more is more preferable, and 0.9 or more is even more preferable. Moreover, 2 or less is preferable, 1.8 or less is more preferable, and 1.6 or less is further more preferable.

[Method for producing hydrogenated block copolymer]
A hydrogenated block copolymer is a polymerization step in which a polymer is obtained by polymerizing at least a conjugated diene compound and a vinyl aromatic hydrocarbon compound using an organic lithium compound as a polymerization initiator in a hydrocarbon solvent. A hydrogenation step of hydrogenating a double bond in a conjugated diene compound unit, a solvent removal step of removing a solvent of a solution containing a hydrogenated block copolymer, and a solvent removal of a partially hydrogenated block copolymer A crumbization step for crumbing can be sequentially performed and manufactured.

  The weight average molecular weight of the partially 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. Further, the weight average molecular weight can also be adjusted by controlling the addition amount of a deactivator described later, once performing a deactivation step, and further continuing the polymerization reaction.

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

(Polymerization process)
The polymerization step is a step of obtaining a polymer by polymerizing a monomer containing at least a conjugated diene compound and a vinyl aromatic hydrocarbon compound in a hydrocarbon solvent using an organic lithium 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 compound is a diolefin having a pair of conjugated double bonds. The conjugated diene compound is not particularly limited. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, Examples include 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 self-adhesion retention of the self-adhesive tape composition. A conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.

The vinyl aromatic hydrocarbon compound is not particularly limited. For example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like can be mentioned. Of these, styrene is preferable from the viewpoint of economy. A vinyl aromatic hydrocarbon compound may be used individually by 1 type, and may use 2 or more types together.
The partially hydrogenated block copolymer may contain a monomer unit other than the vinyl aromatic hydrocarbon compound unit and the conjugated diene compound unit. In the polymerization step, in addition to the vinyl aromatic hydrocarbon compound and the conjugated diene compound, 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, adjustment of the reaction ratio between the conjugated diene compound and the vinyl aromatic hydrocarbon compound, etc. For this purpose, a predetermined polar compound or a randomizing agent can be used.
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, the solution containing the vinyl aromatic-conjugated diene block copolymer having an active terminal is added in an amount such that the functional group is less than 1 molar equivalent with respect to the active terminal. vi) A coupling agent represented by X in (x) to (xiii) 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 molar equivalent with respect to the active end, In some block copolymers among the aromatic vinyl-conjugated diene block copolymers having active ends, the active ends are bonded to each other via a coupling agent residue. 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 compound and / or the vinyl aromatic hydrocarbon compound may be further added after the deactivator is added. By carrying out like this, the polymerization reaction with the active terminal which is not deactivated, and a conjugated diene compound and / or a vinyl aromatic hydrocarbon compound continues, and the polymer solution containing the polymer of a different molecular weight can be obtained.

  In the case of a hydrogenated block copolymer composition comprising partially hydrogenated block copolymers having two different structures, component (A) and component (B), component (A) and component (B) in the deactivation step ) 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.

  Furthermore, after adding the deactivator, a conjugated diene compound and / or a vinyl aromatic hydrocarbon compound is added, and by continuing the polymerization reaction, the ratio of the weight average molecular weight and the weight average molecular weight of the component (A) and the component (B) is increased. Can be controlled. Specifically, as the amount of the conjugated diene compound and / or the vinyl aromatic hydrocarbon compound added after the deactivator is added, the weight average molecular weight of the component (B) increases, and the ratio of the weight average molecular weight accordingly. Tend to be larger.

(Hydrogenation process)
The hydrogenation step is a step of converting a double bond in at least a conjugated diene compound unit 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 aging resistance of the block copolymer composition used for 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 partially hydrogenated block copolymer used in the present 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. Further, 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 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.

((B) Filler)
The composition for self-adhesive tapes of this embodiment contains 1-300 mass parts of fillers. A wide variety of fillers can be selected depending on the intended use and required performance of the resulting self-adhesive tape composition.
The filler is not particularly limited. For example, calcium carbonate, zinc white, aluminum silicate, silica, talc, diatomaceous earth, silica sand, pumice powder, slate powder, mica powder, aluminum sol, alumina white, aluminum sulfate. , Barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, graphite, glass fiber, glass sphere, single crystal potassium titanate, carbon fiber, activated zinc white, zinc carbonate, magnesium oxide, basic magnesium carbonate, resurge, red lead, Examples include lead white, calcium hydroxide, activated calcium hydroxide, calcium oxide, and titanium oxide. Among these fillers, a filler containing calcium, zinc white, silica, and titanium oxide are preferable from the viewpoint of self-adhesion, and a filler containing calcium is more preferable. Among the fillers described above, calcium carbonate is preferable as the filler containing calcium. When these fillers are blended, appropriate cohesiveness can be imparted to the pressure-sensitive adhesive. These fillers can be used individually by 1 type or in combination of 2 or more types.

  Content of a filler is 1-300 mass parts with respect to 100 mass parts of (a) partial hydrogenation block copolymers, Preferably it is 50-250 mass parts, More preferably, it is 75-200 mass parts. It is. When the content of the filler is within the above range, the balance of low adhesive strength, self-adhesion strength, and self-adhesion retention is improved.

((C) Tackifying resin)
It is preferable that the composition for self-adhesive tapes of this embodiment further contains (c) tackifying resin from the viewpoints of adhesive strength and self-adhesive strength. The tackifying resin can be selected from a wide variety depending on the intended use and required performance of the resulting adhesive composition. The tackifying resin is not particularly limited. For example, 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 tackifying resins can be used singly or in combination of two or more.

The tackifying resin may be a liquid type tackifying resin as long as the color tone is colorless to light yellow and has substantially no odor and good thermal stability.
As for content of a tackifier, 4-200 mass parts is preferable with respect to 100 mass parts of (a) partial hydrogenation block copolymers, More preferably, it is 10-150 mass parts, More preferably, it is 20-120. Part by mass. When the content of the tackifying resin is within the above range, the balance of low adhesive strength, self-adhesion strength, and self-adhesion retention is improved.

(Softener)
The softening agent can be added as necessary, and the type is not particularly limited. For example, oils such as known paraffinic, naphthenic, and aromatic process oils and mixed oils thereof, plasticizers, synthetic liquid oligomers, and A mixture thereof may be 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, although content of a softening agent is arbitrary, 1-200 mass parts is preferable.

(Other ingredients)
The adhesive composition of the present embodiment includes, as necessary, an antioxidant, a synthetic rubber or polymer other than the block copolymer constituting the adhesive composition of the present embodiment, a wax, and a light stabilizer. Etc., 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 HP2225FF (trade name), Irgafos 168 (trade name) and Irganox 1520 (trade name), JF77 (trade name) manufactured by Johoku Chemical Co., Ltd. be able to. 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 compositions for self-adhesive adhesive tapes.

  In this specification, “other than the block copolymer used in the present embodiment” means that it does not correspond to any of the block copolymers of the present embodiment. The synthetic rubber or polymer other than the block copolymer used in the present embodiment is not particularly limited. For example, polyolefin resin or vinyl aromatic thermoplastic resin, natural rubber, conjugated diene rubber, ethylene-propylene rubber, Chloroprene rubber, acrylic rubber, polypentenamer rubber, and aromatic vinyl elastomer may be added. 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 copolymers 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 used in the present embodiment, the content of the above synthetic rubber or polymer is arbitrary, but preferably 0 with respect to 100 parts by mass of the composition for self-adhesive adhesive tape. .5 parts by mass or more and 95 parts by mass or less.

  The composition may contain a wax if necessary. The amount of wax added in the composition is preferably 20% by weight or less. If a low melt viscosity, especially a low melt viscosity below 140 ° C. is required, at least one selected from paraffin wax, microcrystalline wax, and Fischer-Tropsch wax having a melting point of 50 ° C. to 110 ° C. It is preferable to contain 2 to 10% by weight of wax. The content is more preferably in the range of 5 to 10% by weight. 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 crystallization temperature of G ′ (measurement conditions: 25 ° C., 10 rad / s) of the obtained composition is preferably 1 Mpa or less, and more preferably 7 ° C. or less.

  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.

[Method of applying composition for self-adhesive adhesive tape]
The method for applying the self-adhesive pressure-sensitive adhesive tape composition is not particularly limited as long as the desired product can be obtained. For example, the self-adhesive pressure-sensitive adhesive tape composition is dissolved in a solvent, and the solution is applied. And a method of coating by a hot melt coating method in which the composition for self-adhesive adhesive tape is melted and coated.
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.

[Self-adhesive adhesive tape]
The self-adhesive adhesive tape of this embodiment is obtained by applying the composition for self-adhesive adhesive tape of this embodiment to at least one surface of a substrate.

〔Base material〕
As the base material, a porous material formed of fibrous materials such as kraft paper, crepe paper, and Japanese paper, or a plastic film formed of polyolefin resin, polyester resin, vinyl chloride resin, polyimide resin, etc. Can be used. When the porous material is used, it can be appropriately treated with an impregnating agent, a back surface treating agent or the like in order to adjust properties such as strength, weather resistance and rigidity. The weight and thickness of the porous material are appropriately selected depending on the application and are not particularly limited.

In addition to the above-described plastic film, the above-mentioned plastic film can be made preferable from the viewpoint of the environment when a biodegradable or photodegradable plastic film is used. Further, a plurality of the above-mentioned ones can be used in combination, and the above-mentioned plastic films can be used together or a plastic film and a porous material can be laminated. Moreover, a porous plastic film can also be used as needed. The plastic film may be subjected to surface treatment such as corona treatment, plasma treatment, and primer treatment on one side or both sides in order to improve adhesion with the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer.
The weighing of the substrate using this plastic film can be used without any particular limitation.

[Use]
The composition for self-adhesive pressure-sensitive adhesive tapes of this embodiment has low adhesive strength, excellent self-adhesion strength, self-adhesion retention, weather resistance, low odor characteristics, and low-temperature characteristics. Taking advantage of such characteristics, it can be suitably used as a self-adhesive tape for binding plants and the like.

  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.

[Characteristics of hydrogenated block copolymer]
<(1-1) Weight average molecular weight>
The weight average molecular weight of the hydrogenated block copolymer is based on the molecular weight of the peak of the chromatogram using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurement of commercially available standard polystyrene. Asked. When the hydrogenated block copolymer 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) 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.

<Content of (1-3) vinyl aromatic 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 monomer unit (styrene) was calculated using a calibration curve.

<(1-4) Content of polymer block mainly composed of vinyl aromatic monomer unit in block copolymer>
I. M.M. Kolthoff, et al. , J. et al. Polym. Sci. , 1946, Vol. 1, p. The content of the polymer block mainly composed of vinyl aromatic monomer units was measured by the osmium tetroxide method described in No. 429 using the following polymer decomposition solution.
(Measurement condition)
Sample to be measured: A sample taken before hydrogenating the polymer Solution for polymer decomposition: A solution in which 0.1 g of osmic acid was dissolved in 125 mL of tertiary butanol

<(1-5) Vinyl, cis, trans bond amount in conjugated diene monomer unit, and hydrogenation rate for each>
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 vinyl, cis, and trans bond amounts and the hydrogenation rate for each were measured.
The conditions for 1H-NMR measurement are described below.

(Measurement condition)
Measuring instrument: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Measurement sample: Extracted sample before and after hydrogenation of polymer Sample concentration: 50 mg / mL
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

<(1-6) Maximum value of loss coefficient tan δ of dynamic viscoelastic spectrum>
The dynamic viscoelastic spectrum was measured by the following method, and the maximum value of the loss coefficient tan δ was obtained.
First, the hydrogenated block copolymer composition was formed into a sheet having a thickness of 2 mm, and then cut into a size having a width of 10 mm and a length of 35 mm, and used as a measurement sample.
A measurement sample is set in the twist type geometry of the device ARES (trade name, manufactured by TI Instrument Co., Ltd.), the effective measurement length is 25 mm, the strain is 0.5%, the frequency is 1 Hz, and the measurement range is −100 ° C. From 100 to 100 ° C. under conditions of a temperature rising rate of 3 ° C./min.

[(2): Measurement of physical properties of composition]
(Adhesive composition (Formulation α, Formulation β, Formulation γ, Formulation θ))
200 parts by mass of Quintone® 100 (manufactured by Nippon Zeon Co., Ltd.) as a tackifier and 100 parts by mass of Diana Process Oil NS-90S (Idemitsu Kosan Co., Ltd.) as a softening agent with respect to 100 parts by mass of a partially hydrogenated block copolymer )) And 5 parts by mass of titanium oxide FTR-700 (manufactured by Sakai Chemical Industry Co., Ltd.) as a filler, and Irganox 1010 (manufactured by BASF Corp.) as an anti-aging agent. One part by mass is mixed and heated using an oil bath, and melt kneaded at 180 ° C. for 60 minutes with a mixer (model: L5M-A, Silverson Nippon Co., Ltd., paddle type four blades) An adhesive composition (formulation α) was obtained.

  150 parts by mass of Alcon M100 (made by Arakawa Chemical Co., Ltd.) as a tackifier and 1 type of zinc oxide as a filler (Sakai Chemical Industry Co., Ltd.) with respect to 100 parts by mass of a partially hydrogenated block copolymer )) And 230 parts by mass of irganox 1010 (BASF Co., Ltd.), an anti-aging agent, and a mixer (model: L5M-A, silver) while heating using an oil bath. Sonnippon Co., Ltd., paddle type four blades) was melt kneaded at 180 ° C. for 60 minutes to obtain a hot melt adhesive composition (formulation β).

  50 parts by mass of Alcon P100 (made by Arakawa Chemical Co., Ltd.) as a tackifier and 100 parts by mass of calcium carbonate super # 1500 (Maruo Calcium Co., Ltd.) as a filler with respect to 100 parts by mass of a partially hydrogenated block copolymer )) And 150 parts by mass of Irganox 1010 (BASF Co., Ltd.) which is an anti-aging agent, 600 parts by mass of toluene, and a mixer (model: L5M-A, The mixture was stirred for 60 minutes with Silverson Nippon Co., Ltd. (paddle type 4 blades) to obtain a solvent-type adhesive composition (formulation γ).

  50 parts by mass of Alcon P100 (made by Arakawa Chemical Co., Ltd.) that is a tackifier and 100 parts by mass of silica ST-CROWN (Shiraishi Calcium Co., Ltd.) that is a filler with respect to 100 parts by mass of the partially hydrogenated block copolymer crumb )) And 150 parts by mass of Irganox 1010 (BASF Co., Ltd.) which is an anti-aging agent, 600 parts by mass of toluene, and a mixer (model: L5M-A, A solvent type adhesive composition (formulation θ) was obtained by stirring for 60 minutes with Silverson Nippon Co., Ltd. (paddle type 4 blades).

<(2-1) Low Odor Characteristic Evaluation of Adhesive Composition (Formulation α, Formulation β, Formulation γ, Formulation θ)>
The low odor characteristic was evaluated by a sensory test. Ten minutes after a specific amount of the composition was put into a 14 cm × 8 cm PE bag and sealed, the smell in the bag was smelled, and the smell was felt as odor. Based on the obtained results, the low odor characteristics were evaluated according to the following criteria.
If the adhesive composition does not feel odor even if it is 20 g or more: ◎
When the adhesive composition is 10 g or more and less than 20 g and does not feel odor: ○ When the adhesive composition is 5 g or more and less than 10 g and does not feel odor: Δ
When the adhesive composition is less than 5 g and feels odor: ×

(Production of adhesive tape)
The hot melt 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.
The solvent-type adhesive composition was 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 the pressure-sensitive adhesive layer had a thickness of 40 μm. An adhesive tape was prepared.

<(2-2) Probe tack of adhesive composition (Formulation α, Formulation γ, Formulation β, Formulation θ)>
The probe tack was measured according to ASTM D2979. After sticking the adhesive tape to the weight (load 10 g) at a temperature of 23 ° C., the probe (5 mmφ) is brought into contact with the adhesive tape at a speed of 1 mm / sec. One second later, the probe was peeled off at a speed of 1 mm / sec, the maximum value at that time was measured, and tack was evaluated. The evaluation is ◎, ○, Δ, × from the best order.
0.6> Probe tack (N / 5mmφ): ◎
1.2> Probe tack (N / 5 mmφ) ≧ 0.6: ○
2.0> probe tack (N / 5mmφ) ≧ 1.2: Δ
Probe tack (N / 5mmφ) ≧ 2.0: ×

<(2-3) Adhesive strength of adhesive composition (Formulation α, Formulation γ, Formulation β, Formulation θ)>
At a temperature of 23 ° C., a 25 mm wide adhesive tape was affixed to a 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.
Adhesive strength (N / 10 mm) <4: ◎
4 ≦ adhesive strength (N / 10 mm) <7: ○
7 ≦ Adhesive strength (N / 10 mm) <13: Δ
13 ≦ Adhesive strength (N / 10 mm): ×

<(2-4) Self-adhesive strength of adhesive composition (Formulation α, Formulation γ, Formulation β, Formulation θ)>
At a temperature of 23 ° C. and 5 ° C., the adhesive surface of a 10 mm wide adhesive tape is used as the inside, and the adhesive is bonded so that the bonding length is 100 mm or more, and T-type peeling is performed at a peeling speed of 300 mm / min. The peel strength (N / 10 mm) obtained was evaluated. The evaluation is ◎, ○, Δ, × from the best order.
(Under 23 ° C atmosphere)
15 ≦ self-adhesive force (N / 10 mm): ◎
10 ≦ self-adhesion force (N / 10 mm) <15: ○
7 ≦ self-adhesion force (N / 10 mm) <10: Δ
Self-adhesive force (N / 10 mm) <7: ×
(Under 5 ° C atmosphere)
13 ≦ Self-adhesive force (N / 10 mm): ◎
8 ≦ self-adhesion force (N / 10 mm) <13: ○
4 ≦ self-adhesion force (N / 10 mm) <8: Δ
Self-adhesive force (N / 10 mm) <4: ×

<(2-5) Self-adhesion retention of adhesive composition (Formulation α, Formulation γ, Formulation β, Formulation θ)>
The self-adhesive adhesive tape having a width of 10 mm and a length of 100 mm is left as the adhesive adhesive tape having a length of 20 mm at both ends, and the same self-adhesive as the above-mentioned self-adhesive adhesive tape having a length of 60 mm in the adhesive portion of 60 mm in the center. A self-adhesive pressure-sensitive adhesive tape test piece was obtained by applying a self-adhesive tape to make it non-tacky. Adhering the 20 mm long pressure-sensitive adhesive parts at both ends of the above test piece, inserting a metal support rod having a diameter of 15 mm into the loop portion and supporting it, hanging a weight of 1000 g in weight, The dropping time of the weight was evaluated in a state where the temperature was 50 ° C. Evaluation shall be (circle), (triangle | delta), and x from a favorable order.
120 ≦ retention force (50 ° C.) (minutes) <600: ○
30 ≦ holding force (50 ° C.) (minutes) <120: Δ
Holding power (50 ° C.) (minutes) <30: ×

<Weather resistance of (2-6) adhesive composition (Formulation α, Formulation γ, Formulation β, Formulation θ)>
Using a sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., a sample with a 25 mm wide adhesive tape attached to a SUS plate was used at an ambient temperature of 43 ° C., 50% RH, a black panel temperature of 63 ° C., and a rainfall of 12 minutes / 1 hour. After treatment for 24 hours under the conditions, the film was peeled off at a temperature of 23 ° C. 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.
Adhesive strength (N / 10 mm) <4: ◎
4 ≦ adhesive strength (N / 10 mm) <7: ○
7 ≦ Adhesive strength (N / 10 mm) <13: Δ
13 ≦ Adhesive strength (N / 10 mm): ×

[(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 block copolymer]
<Production Examples 1-4>
A stainless steel autoclave with a stirrer and a jacket was washed, dried and purged with nitrogen, charged with cyclohexane, and warm water was passed through the jacket to set the contents at 70 ° C. N, N, N ′, N′-tetramethylethylenediamine and n-butyllithium cyclohexane solution were added, and a cyclohexane solution containing 15 parts by mass of styrene was continuously added. The polymerization conversion of styrene was 100%. Subsequently, a cyclohexane solution containing 85 parts by mass of 1,3-butadiene was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 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, methanol was added to inactivate. At this stage, a part of the polymer solution was extracted to obtain the block copolymer of Production Example 1.

  The hydrogenation catalyst prepared as described above was added at 100 ppm based on Ti based on 100 parts by mass of the block copolymer, a hydrogenation reaction was performed to obtain a partially hydrogenated block copolymer, and a part of the polymer solution was extracted. A block copolymer of Polymer Production Example 2 was obtained. The polymer solution remaining in the reactor was further subjected to hydrogenation reaction to obtain a partially hydrogenated block copolymer, and the block copolymer of Polymer Production Example 3 was obtained. The polymer solution remaining in the reactor was further subjected to a hydrogenation reaction to the end point to obtain a completely hydrogenated block copolymer, and a block copolymer of Polymer Production Example 4 was obtained.

<Production Examples 5 and 6>
A block copolymer of Production Example 5 was obtained in the same manner as Production Example 3, except that the addition amount of styrene was changed to 8 parts by mass and the addition amount of 1,3-butadiene was changed to 92 parts by mass. Further, the block copolymer of Production Example 6 was obtained in the same manner as Production Example 3 except that the addition amount of styrene was changed to 25 parts by mass and the addition amount of 1,3-butadiene was changed to 75 parts by mass.
The resulting copolymer is shown in Table 1.

<Examples 1-4, Comparative Examples 1-3>
Using the block copolymers of Production Examples 1 to 6 and SIS (D1161 Kraton Co., Ltd.), a hot-melt adhesive composition (formulation α) 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 2.

<Examples 5-8, Comparative Examples 4-6>
Using the block copolymers of Production Examples 1 to 6 and SIS (D1161 Kraton Co., Ltd.), a hot-melt adhesive composition (formulation β) 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.

<Examples 9 to 13 and Comparative Examples 7 to 9>
Using the block copolymers of Production Examples 1 to 6 and SIS (D1161 Kraton Co., Ltd.), a hot-melt adhesive composition (formulation γ) was obtained by the above-described method for producing an adhesive composition. Moreover, the solvent-type adhesive composition (compound | blending (theta)) shown in Example 13 was obtained by the preparation method of the adhesive composition mentioned above using the block copolymer of manufacture example 3. FIG. 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 4.

  The self-adhesive tape composition of the present embodiment can be suitably used as a hot-melt adhesive, a solvent-type adhesive, particularly a self-adhesive tape that binds plants and the like.

Claims (4)

Following component (a), a self-adhesive tape composition comprising a component (b), and component (c),
(A) 100 parts by mass of partially hydrogenated block copolymer (b) 1 to 300 parts by mass of filler
(C) 4 to 200 parts by mass of tackifying resin The (a) partially hydrogenated block copolymer comprises a polymer block Ar mainly composed of vinyl aromatic hydrocarbon compound units and a conjugated diene compound unit. Having a polymer block D as a main component,
Unsaturated double bond hydrogenation ratio derived from the conjugated diene compound unit is Ri 10～90Mol% der,
The weight average molecular weight is 20,000 or more and 1,000,000 or less,
The content of the vinyl aromatic hydrocarbon block polymer is 10 to 50% by mass,
Before hydrogenation, the vinyl bond amount of the conjugated diene compound unit is 10 to 80 mol%, the cis and trans bond content of the conjugated diene compound unit is 20 to 90 mol%,
It contains component (A) and component (B) which are partially hydrogenated block copolymers having two different structures, and (weight average molecular weight of component (B)) / (weight average molecular weight of component (A)) is 1. .3～10 der Ru, self-adhesive tape composition. Wherein (b) is a filler containing calcium, self-adhesive adhesive tape composition of claim 1. In the partially hydrogenated block copolymer (a), the content of the vinyl aromatic hydrocarbon compound unit is 10 to 20% by mass, and the cis and trans bonds in the conjugated diene compound unit before hydrogenation are 5 to 25 mol. The composition for self-adhesive pressure-sensitive adhesive tapes according to claim 1 or 2 , which is hydrogenated in a range of%. The self-adhesive adhesive tape which apply | coated the composition as described in any one of Claims 1-3 to one surface of a base material.