JP2017197609A - Adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film excellent in initial adhesiveness, low temperature adhesiveness, feedability, low adhesive disease resisting property, and characteristic balance.SOLUTION: A tube has an adhesive layer containing a hydrogenated block copolymer (a) on a base material film, where (a) contains a polymer block (C) containing a conjugated diene compound as a main component, a polymer block (B) containing a conjugated compound as a main component and a polymer block (S) containing an aromatic vinyl compound as a main component, (B) contains polymer blocks (B1) and (B2), and in (a), a content of (C) is 1-20 mass%, a content of (B) is 73-97 mass%, a content of (S) is 1-15 mass%, a vinyl bond amount of (C) before hydrogenation is 1-25 mol%, a vinyl bond amount of (B1) before hydrogenation is 40-60 mol%, a vinyl bond amount of (B2) before hydrogenation is more than 60 mol% and 100 mol% or less, and a hydrogenation ratio is 80 mol% or more.SELECTED DRAWING: None

Description

  The present invention relates to an adhesive film.

Surface protective film is polarizing plate, retardation film, light guide plate, optical film for LCD, sheet, touch panel substrate film, antireflection film for PDP, optical protective film used for surface protection of optical members, steel plate for automobiles, etc. It is used in a wide variety of fields, such as protective films and protective films for various plastics. From the viewpoint of preventing scratches and dirt on the surface during processing, transportation and transportation, the surface protective film is affixed and processed Or it is common to peel off and use the surface protection film which concerns after transportation conveyance.
Therefore, an appropriate pressure-sensitive adhesive characteristic according to the application is required.

  For example, if the adhesive strength is too high, a large force is required for peeling off, which may cause problems that workability is poor and feeding performance is deteriorated. On the other hand, if the adhesive strength is too low, a problem of peeling during storage may occur. Therefore, it is preferable to have an adhesive property corresponding to the use of the surface protective film.

Conventionally, rubber-based pressure-sensitive adhesives mainly composed of rubbers such as acrylic pressure-sensitive adhesives, natural rubbers, and polyisobutylenes are mainly used as pressure-sensitive adhesives used for the surface protective film pressure-sensitive adhesive layer.
As a method of applying these pressure-sensitive adhesives to a predetermined support film, a method of applying a pressure-sensitive adhesive solution obtained by dissolving a pressure-sensitive adhesive in a solvent using a roll, a spray or the like is used. These methods have the advantage that the pressure-sensitive adhesive layer can be applied uniformly and thinly. It is not preferable.

On the other hand, it can be manufactured by extrusion molding, there is no risk of fire and pollution during manufacturing with solvents, there are few manufacturing processes, it is economical, and it has excellent molding processability. Development has been made on a pressure-sensitive adhesive laminate having appropriate adhesion and good peelability.
For example, Patent Document 1 discloses a pressure-sensitive adhesive laminate having a base material layer (A) and an adhesive layer (B) on one side of the base material layer, wherein the adhesive layer (B) is at least one kind of vinyl. Aromatic compound polymer block (A), random copolymer block of vinyl aromatic compound and conjugated diene or conjugated diene compound polymer block (B), and polybutadiene having 1,2-vinyl bond are 30% by weight or less A pressure-sensitive adhesive laminate comprising a hydrogenated diene copolymer (1) obtained by hydrogenating a conjugated diene portion of a diene copolymer in which the polybutadiene block (C) is block-bonded and an olefin resin (2) is disclosed. Has been.

Japanese Patent Laid-Open No. 10-102014

  However, as a result of intensive studies by the inventors, in the pressure-sensitive adhesive laminate as described in Patent Document 1, as the surface protective film, the initial pressure-sensitive adhesiveness, the low-temperature pressure-sensitive adhesiveness, the payout property, the low pressure-sensitive adhesive property, and these It was found that there is room for improvement in the balance of characteristics.

Therefore, in the present invention, in view of the problems of the above-described conventional technology, the adhesive layer contains a hydrogenated block copolymer (a) having a specific structure, and has initial adhesiveness, low-temperature adhesiveness, pay-out property, and low adhesiveness. An object is to provide a pressure-sensitive adhesive film excellent in progress and balance of these properties.
That is, the present invention is as follows.

[1]
On the base film,
An adhesive film comprising an adhesive layer comprising a hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) is in the molecule,
A polymer block (C) mainly composed of a conjugated diene compound;
A polymer block (B) mainly composed of a conjugated diene compound;
A polymer block (S) mainly composed of an aromatic vinyl compound;
Including,
The polymer block (B) includes polymer blocks (B1) and (B2),
In the hydrogenated block copolymer (a), the content of the polymer block (C) is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, The content of the polymer block (S) is 1 to 15% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C) is 1 to 25 mol%, the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less, The vinyl bond amount before hydrogenation of the combined block (B2) is more than 60 mol% and 100 mol% or less,
The hydrogenation rate is 80 mol% or more,
Adhesive film.
[2]
In 100 mass% of the hydrogenated block copolymer (a), the total content of the polymer block (C) and the polymer block (S) is 3 to 27 mass%.
The adhesive film as described in [1] above.
[3]
The content of the polymer block (B1) in 100% by mass of the polymer block copolymer (a) is 10 to 60% by mass, and the content of the polymer block (B2) is 30 to 80% by mass. %
The adhesive film according to [1] or [2].
[4]
On the base film,
An adhesive film comprising an adhesive layer comprising a hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) contains an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule,
The content of the aromatic vinyl compound unit of the hydrogenated block copolymer (a) is 1 to 15% by mass,
The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more,
The amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units in the hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) has a crystallization peak at −20 to 80 ° C., and the crystallization heat quantity is 0.1 to 10 J / g,
The elution amount peak of the hydrogenated block copolymer (a) measured by thermal gradient interaction chromatography (TGIC) is in the range of 0 ° C. or higher and 150 ° C. or lower,
The half-value width of the elution peak is in the range of 20 to 40 ° C.
The hydrogenated block copolymer (a) has a Shore A hardness of 15 to 60,
Adhesive film.
[5]
Tan δ showing the glass transition of the hydrogenated block copolymer (a) observed in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (1 Hz) of the hydrogenated block copolymer (a) The peak (Tg1) is in the range of more than −45 ° C. and not more than −30 ° C., and the tan δ peak observed when 30% by mass of the hydrogenated block copolymer (a) is added to homopolypropylene ( The difference ΔTg (Tg1−Tg2) from Tg2) is 3 to 12 ° C.,
The adhesive film according to any one of [1] to [4].
[6]
Ratio of integrated value of 29.4 to 30.0 ppm measured by 13C-NMR and integrated value of 9.0 to 14.0 ppm (integrated value of 29.4 to 30.0 ppm / 9.0 to 14.0 ppm) Integration value)
It is in the range of the integral value obtained by the following equation (2) from the ratio of the integral value obtained by the following equation (1),
The amount of butylene is 50 to 80 mol%,
The adhesive film according to any one of [1] to [5].
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)
[7]
The adhesive layer further comprises 5 to 95% by mass of a hydrogenated block copolymer (b) and / or a hydrogenated block copolymer (c),
The hydrogenated block copolymer (b) is in the molecule,
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b),
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 95 to 70% by mass,
The content of the polymer block (S1) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 30 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b) is 80 mol% or more,
The hydrogenated block copolymer (c) is in the molecule,
A polymer block (B-2) comprising a conjugated diene compound and a vinyl aromatic compound;
A polymer block (S2) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (c),
The content of the polymer block (B-2) containing the conjugated diene compound and the vinyl aromatic compound is 95 to 70% by mass,
The content of the polymer block (S2) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The hydrogenation rate of the hydrogenated block copolymer (c) is 80 mol% or more,
The adhesive film according to any one of [1] to [6].
[8]
The adhesive layer is
The pressure-sensitive adhesive film according to any one of [1] to [7], including a tackifier in an amount of 0.5 to 50% by mass.
[9]
The tackifier is
The adhesive film according to [8], which is at least one selected from the group consisting of hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene phenol resins, and terpene phenol resins.
[10]
The polymer block (B) further includes a polymer block (B3) present at the terminal of the hydrogenated block copolymer (a),
The content of the polymer block (B3) is 1 to 10% by mass in the hydrogenated block copolymer (a).
The adhesive film according to any one of [1] to [9].
[11]
The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is 100,000 to 300,000.
The adhesive film according to any one of [1] to [10].
[12]
The adhesive film according to any one of [1] to [11], wherein the microphase separation structure of the hydrogenated block copolymer (a) forms a spherical structure (sphere structure).

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive film excellent in initial stage adhesiveness, low temperature adhesiveness, pay-out property, low adhesive progressability, and these characteristic balance can be provided.

The graph which shows the relationship between the ratio represented by the amount of butylenes of a hydrogenated block copolymer and the integral value of 29.4-30.0 ppm / 9.0-14.0 ppm is shown. The transmission electron microscope (TEM) image of an example of a hydrogenation block copolymer is shown. The transmission electron microscope (TEM) image of another example of a hydrogenation block copolymer is shown.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

[Adhesive film]
The pressure-sensitive adhesive film of this embodiment is a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer containing a hydrogenated block copolymer (a) described later on a base film.
By having the said structure, the adhesive film excellent in initial adhesiveness, low-temperature adhesiveness, pay-out property, low adhesive progressability, and these characteristic balance is obtained.

(Base film)
It does not specifically limit as a material of a base film, Either nonpolar resin and polar resin can be used.
In view of performance and price, the nonpolar resin can be exemplified by polyethylene, homo- or block polypropylene, and the polar resin can be exemplified by polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, ethylene- A vinyl acetate copolymer, its hydrolyzate, etc. can be illustrated as a preferable thing.

The thickness of the base film is preferably 1 mm or less, more preferably 300 μm or less, and even more preferably 10 to 200 μm.
When the thickness of the base film is 10 μm or more, the adherend can be sufficiently protected, and when the thickness of the base film is 1 mm or less, a practically good elastic modulus is obtained, and good unevenness is obtained. Followability can be obtained, and floating and peeling can be effectively prevented.

(Adhesive layer)
The adhesive film of this embodiment comprises an adhesive layer containing a hydrogenated block copolymer (a) on the substrate film.
The pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive film of the present embodiment preferably has a thickness of 3 to 100 μm. As for the thickness of the adhesion layer, it is more preferable that it is 5-50 micrometers, and it is further more preferable that it is 8-20 micrometers.
When the thickness of the pressure-sensitive adhesive layer is 100 μm or less, the handling property tends to be excellent, which is also economically preferable. Moreover, it exists in the tendency for it to be excellent in adhesiveness by being 3 micrometers or more, and to obtain uniform thickness.
In general, a sheet-like molded body having a thickness of 0.005 mm or more and less than 0.2 mm is referred to as a film, and a sheet-like molded body having a thickness of 0.2 mm or more and 50 mm or less is referred to as a sheet. The “film” includes the above film and sheet.

<Hydrogenated block copolymer (a)>
In the molecule, the hydrogenated block copolymer (a) contained in the adhesive layer of the adhesive film of the present embodiment is
A polymer block (C) mainly composed of a conjugated diene compound;
A polymer block (B) mainly composed of a conjugated diene compound;
A polymer block (S) mainly composed of an aromatic vinyl compound;
Including,
The polymer block (B) includes polymer blocks (B1) and (B2),
In the hydrogenated block copolymer (a), the content of the polymer block (C) is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, The content of the polymer block (S) is 1 to 15% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C) is 1 to 25 mol%, the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less, The vinyl bond amount before hydrogenation of the combined block (B2) is more than 60 mol% and 100 mol% or less,
The hydrogenation rate is 80 mol% or more.

The hydrogenated block copolymer (a) has an elution amount peak measured by thermal gradient interaction chromatography (hereinafter referred to as “TGIC”) in the range of 0 ° C. to 150 ° C., and the half-value width of the elution peak. Is preferably in the range of 20-40 ° C,
The hydrogenated block copolymer (a) preferably has a Shore A hardness of 15 to 60.
Specifically, the elution amount peak measured by thermal gradient interaction chromatography (TGIC) on a dried sample of the hydrogenated block copolymer (a) or the Soxhlet extract of the adhesive film of this embodiment is 0 ° C. or higher and 150 ° C. It exists in the following ranges, and the half value width of an elution amount peak is the range of 20-40 degreeC.
By having the above behavior, it is possible to improve the initial adhesiveness, payout property, and low adhesive progress property balance of the obtained adhesive film.
From the same viewpoint, the half width of the elution peak in the range of 0 ° C. or higher and 150 ° C. or lower is more preferably 21 to 37 ° C., further preferably 22 to 34 ° C.
The half-width of the TGIC elution amount peak can be controlled by adjusting the ratio of the polymer blocks (C), (B1), and (B2) within the above-described range. The TGIC elution amount is an example described later. It can be measured by the method described in 1.
In addition, the said half value width originates in the structure of hydrogenated block copolymer (a), and when the measurement conditions are the same, when hydrogenated block copolymer (a) is used for a measurement sample, When the film containing the hydrogenated block copolymer is used as the measurement sample, the half-value width of the elution amount peak does not change.

Moreover, the hydrogenated block copolymer (a) mentioned above can also be specified as follows.
That is, the hydrogenated block copolymer (a) includes an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule, and the content of the aromatic vinyl compound unit is 1 to 15% by mass, The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more, and the amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units, and the hydrogen The crystallization block copolymer (a) has a crystallization peak at -20 to 80 ° C., and the crystallization heat quantity is 0.1 to 10 J / g,
The hydrogenated block copolymer (a) has an elution peak measured by thermal gradient interaction chromatography (hereinafter referred to as “TGIC”) in the range of 0 ° C. or higher and 150 ° C. or lower. Is in the range of 20-40 ° C,
The hydrogenated block copolymer (a) has a Shore A hardness of 15 to 60.
Since it is comprised as mentioned above, the adhesive film of this embodiment is excellent in initial stage adhesiveness, low temperature adhesiveness, pay-out property, low adhesive progress, and these property balance.

The hydrogenated block copolymer (a) contained in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present embodiment contains a polymer block (C) (hereinafter simply referred to as “polymer block ( C) ”), a polymer block (B) mainly composed of a conjugated diene compound (hereinafter also simply referred to as“ polymer block (B) ”), and an aromatic vinyl compound mainly. Polymer block (S) (hereinafter also simply referred to as “polymer block (S)”).
Here, “mainly” means that the target monomer unit is contained in an amount of 60% by mass or more in the target polymer block.
From the viewpoint of initial tackiness and low-temperature tackiness of the resulting tacky film, the content of the conjugated diene compound in the polymer block (C) and polymer block (B) mainly composed of the conjugated diene compound is independent of each other. Preferably, it is 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
Further, from the viewpoint of the payout property of the resulting adhesive film and the low adhesion progress, the content of the vinyl aromatic compound in the polymer block (S) mainly composed of the vinyl aromatic compound is preferably 70% by mass or more. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
The content of the conjugated diene compound and the content of the vinyl aromatic compound can be measured by nuclear magnetic resonance spectrum analysis (NMR).
The conjugated diene compound unit is a unit constituting the hydrogenated block copolymer (a) and means a structural unit derived from the monomer of the conjugated diene compound. Moreover, an aromatic vinyl compound unit is a unit which comprises a hydrogenated block copolymer (a), Comprising: The structural unit derived from the monomer of an aromatic vinyl compound is said.

The “vinyl bond amount before hydrogenation” in the polymer blocks (C) and (B) is the bond mode of 1,2-bond, 3,4-bond and 1,4-bond of the conjugated diene before hydrogenation The ratio (mol%) of what is incorporated in 1,2-bond and 3,4-bond is incorporated.
The amount of vinyl bonds can be measured by nuclear magnetic resonance spectrum analysis (NMR).

In the adhesive film of this embodiment, the conjugated diene used in the polymer blocks (C) and (B) in the hydrogenated block copolymer (a) is a diolefin having a pair of conjugated double bonds. is there.
Examples of the diolefin include, but are not limited to, 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, 1,3-hexadiene, and farnesene.
Particularly common diolefins include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
The polymer block (C) is made of butadiene, and the polymer block (B) is made of butadiene or isoprene, from the viewpoints of initial adhesiveness and low-temperature adhesiveness of the adhesive film of this embodiment. Is preferred.

In the present embodiment, the aromatic vinyl compound used in the polymer block (S) in the hydrogenated block copolymer (a) is not limited to the following, but for example, styrene, α-methyl Examples thereof include aromatic vinyl compounds such as styrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene.
Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferably used from the viewpoints of availability and productivity. Particularly preferred is styrene.
The polymer block (S) may be composed of one type of aromatic vinyl compound unit or may be composed of two or more types.

The content of the polymer block (C) in the hydrogenated block copolymer (a) is 1 to 20% by mass from the viewpoints of initial tackiness, low-temperature tackiness, feedability, and low tackiness. .
From the same viewpoint, the content of the polymer block (C) in the hydrogenated block copolymer (a) is preferably 2 to 15% by mass, more preferably 3 to 10% by mass. Content of a polymer block (C) can be measured by the method described in the Example mentioned later.

The amount of vinyl bonds before the hydrogenation of the polymer block (C) (hereinafter also simply referred to as “vinyl amount”) is the appropriate initial tackiness, low-temperature tackiness, feedability, and From the viewpoint of low adhesion progress, it is 1 mol% or more and 25 mol% or less.
From the same viewpoint, the vinyl bond amount before hydrogenation of the polymer block (C) is preferably 3 to 22 mol%, more preferably 5 to 20 mol%.
Specifically, the amount of vinyl bonds before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled by using a vinylating agent such as a polar compound, Lewis base, ether, amine or the like.

The content of the polymer block (B) in the hydrogenated block copolymer (a) is 73 from the viewpoint of initial tackiness, low-temperature tackiness, pay-out property, and low tackiness of the resulting tacky film. It is -97 mass%.
From the same viewpoint, the content of the polymer block (B) is preferably 75 to 95% by mass, more preferably 82 to 93% by mass. Content of a polymer block (B) can be measured by the method described in the Example mentioned later.

In this embodiment, the vinyl bond amount before hydrogenation of the polymer block (B) is specified for each of the polymer block (B1) and the polymer block (B2) included in the block.
That is, the vinyl bond amount before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less from the viewpoint of low-temperature adhesiveness, pay-out property, and low-adhesion progress of the adhesive film of this embodiment. . From the same viewpoint, the vinyl bond amount before hydrogenation of the polymer block (B1) is preferably 42 to 58 mol%, more preferably 45 to 55 mol%.
Moreover, the vinyl bond amount before hydrogenation of a polymer block (B2) is more than 60 mol% and 100 mol% or less from a viewpoint of the initial adhesiveness of the adhesive film of this embodiment. From the same viewpoint, the amount of vinyl bonds before hydrogenation of the polymer block (B2) is preferably 65 to 95 mol%, more preferably 70 to 90 mol%.
Specifically, the amount of vinyl bonds before hydrogenation of the polymer block (B) mainly composed of the conjugated diene compound can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled by using a vinylating agent such as a polar compound, Lewis base, ether, amine or the like.

As described above, the hydrogenated block copolymer (a) includes the polymer block (C) and the polymer block (B), thereby including at least three polymer blocks having different vinyl contents.
That is, the polymer block (C) that contributes to low drawability and low adhesion progress with a low vinyl content of 1 to 25 mol%; Combined block (B1); and having a polymer block (B2) that has a high vinyl content and contributes to the initial adhesiveness, more than 60 mol% and 100 mol% or less, combined with the characteristics of each polymer block, the initial adhesiveness It is particularly excellent in the balance of low-temperature adhesiveness, pay-out property, and low-adhesive progress.
That is, when the adhesive film of this embodiment contains the hydrogenated block copolymer (a), the “initial adhesiveness” and the “feeding-out property, and the low adhesiveness, which have been conventionally considered to have a trade-off relationship, are considered. The balance with “progressiveness” is particularly good, and sufficient tackiness can be imparted even at low temperatures.

In the pressure-sensitive adhesive film of the present embodiment, the hydrogenated polymer block copolymer (a) 100 mass from the viewpoint of the balance of various properties of the initial pressure-sensitive adhesive property, low-temperature pressure-sensitive adhesive property, pay-out property, and low-adhesive property of the pressure-sensitive adhesive film. % Of the polymer block (B1) is preferably 10 to 60% by mass, and the content of the polymer block (B2) is preferably 30 to 80% by mass.
From the same viewpoint, the content of the polymer block (B1) is more preferably 15 to 55% by mass, and the content of the polymer block (B2) is more preferably 40 to 75% by mass. . Further, the content of the polymer block (B1) is more preferably 20 to 50% by mass, and the content of the polymer block (B2) is further preferably 50 to 70% by mass. These contents can be measured by the method described in Examples described later.

The content of the polymer block (S) in the hydrogenated block copolymer (a) is 1 to 15% by mass from the viewpoints of appropriate initial tackiness, payout property, and low tackiness of the tacky film. is there.
From the same viewpoint, the content of the polymer block (S) is preferably 2 to 12% by mass, more preferably 3 to 9% by mass.
Content of the polymer block (S) in a hydrogenated block copolymer can be measured by the method described in the Example mentioned later.

The content of the aromatic vinyl compound unit of the hydrogenated block copolymer (a) is 1 to 15% by mass from the viewpoints of appropriate initial tackiness of the pressure-sensitive adhesive film, feedability, and low tackiness, Preferably it is 2-12 mass%, More preferably, it is 3-9 mass%.
Content of the aromatic vinyl compound unit in hydrogenated block copolymer (a) can be measured by the method described in the Example mentioned later.
In the hydrogenated block copolymer (a), the amount of butylene and / or propylene with respect to the total 100 mol% of the conjugated diene compound units is the initial tackiness, low-temperature tackiness, feedability, and low tackiness of the tacky film. From the viewpoint of balance of various characteristics of the progressive property, it is 42 to 80 mol%, preferably 45 to 80 mol%, more preferably 55 to 70 mol%.
The amount of butylene and / or propylene can be measured by the method described in Examples described later.
The amount of butylene and / or propylene can be controlled by the use of a vinyl compound such as a polar compound, Lewis base, ether, amine, and the hydrogenation rate.

  In the adhesive film of the present embodiment, the polymer block (C) and the polymer block (S) in the hydrogenated block copolymer (a) are used from the viewpoints of initial adhesiveness, pay-out property, and low adhesive progress. The total content is preferably 3 to 27% by mass, more preferably 5 to 25% by mass, and even more preferably 7 to 18% by mass.

Although the structure of the hydrogenated block copolymer (a) of this embodiment is not specifically limited, For example, what has a structure represented by a following formula is mentioned.
(CB) _n -S
(CBS) _n
(C-B-S) _n- (B3)
(C-B-S- (B3)) _n
(C-B-S) _m -X
(C-B-S- (B3)) _m- X
(In the above formula, C, B, S and B3 respectively represent polymer blocks (C), (B) and (S) and (B3) which will be described later. One B is at least one polymer block (B1) or polymer block (B2), and may be composed of a plurality of polymer blocks (B1) and a polymer block (B2). In the case where only one B exists, B consists of at least one polymer block (B1) and at least one polymer block (B2).
n is 1 or more, preferably an integer of 1 to 3. m shows 2 or more, Preferably it is an integer of 2-6. X represents a coupling agent residue or a polyfunctional initiator residue. )
In particular, a polymer represented by a structural formula of C—B—S or C—B—S— (B 3) is preferable.

In the adhesive film of the present embodiment, from the viewpoint of initial adhesiveness, a polymer in which a polymer block polymer block (B) mainly composed of a conjugated diene is present at the terminal of the hydrogenated block copolymer (a) The block (B3) is further included, and the content of the polymer block (B3) in the hydrogenated block copolymer (a) is preferably 1 to 10% by mass.
From the same viewpoint, the content of the polymer block (B3) is more preferably 1.5 to 7% by mass and 2 to 5% by mass in the hydrogenated block copolymer (a). Further preferred.
The content of the polymer block (B3) present at the terminal of the hydrogenated block copolymer (a) can be controlled by the feed composition of the polymerization monomer.

The hydrogenation rate of the hydrogenated block copolymer (a), that is, the hydrogenation rate of all conjugated diene compound units contained in the hydrogenated block copolymer (a) is 80 mol% or more, preferably 85 mol%. It is above, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more.
The hydrogenation rate of all unsaturated group units contained in the conjugated diene monomer unit of the hydrogenated block copolymer (a) can be measured by nuclear magnetic resonance spectrum analysis (NMR), and specifically described later. It can be measured by the method described in the examples.

  By setting the hydrogenation rate to 80 mol% or more, crystallization of the polymer block (C) is enhanced, the blocking resistance of the hydrogenated block copolymer is improved, and the adhesive film of the present embodiment The characteristic balance of initial tackiness, pay-out property, and low tackiness is good.

  The hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, and the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, pressure and temperature.

The hydrogenated block copolymer (a) has a crystallization peak at -20 to 80 ° C. from the viewpoint of blocking resistance, the payout property of the resulting adhesive film, and low adhesion progress, and the crystallization heat amount. Is 0.1 to 10 J / g.
From the same viewpoint, the temperature range in which the crystallization peak is present is preferably −10 to 70 ° C., and more preferably 0 to 60 ° C. The crystallization heat amount is preferably 1.0 to 7.5 J / g, and more preferably 1.5 to 5.0 J / g.
The temperature range in which the crystallization peak exists and the amount of crystallization heat can be measured by the method described in the examples described later.
The crystallization peak temperature range and crystallization heat amount of the hydrogenated block copolymer (a) are determined based on the content of the polymer block (C) and the use of a vinyl compound such as a polar compound, Lewis base, ether, amine, etc. The hydrogenation rate can be controlled.

In the pressure-sensitive adhesive film of this embodiment, the microphase separation structure of the hydrogenated block copolymer (a) contained in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film has a size of 5 from the viewpoints of pay-out property and low-adhesion progress. It is preferable to include a sphere structure (sphere structure) of ˜20 nm.
In the hydrogenated block copolymer (a), the sphere structure is a unique structure observed when the content of the polymer block (S) is within a predetermined range and is present at one end, It can confirm by the method as described in the Example mentioned later.

In this embodiment, the melt flow rate (MFR; conforming to ISO 1133) of the hydrogenated block copolymer (a) is low in workability, initial tackiness, feedability, and lowness of the tacky film of this embodiment. From the viewpoint of adhesive progress, etc., it is preferably 0.1-30 g / 10 minutes, more preferably 0.5-15 g / 10 minutes or less, and further more preferably 1-10 g / 10 minutes or less. preferable.
The melt flow rate is the molecular weight of the hydrogenated block copolymer (a), the content of vinyl aromatic monomer units, the amount of vinyl bonds in the conjugated diene part, the hydrogenation rate, the hydrogenated block copolymer (a) It can be controlled by adjusting the block structure or the like.

In this embodiment, from the viewpoint of low-temperature adhesiveness of the obtained adhesive film, it is observed in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (1 Hz) of the hydrogenated block copolymer (a). The tan δ peak (Tg1) indicating the glass transition of the hydrogenated block copolymer (a) is preferably in the range of more than −45 ° C. and not more than −30 ° C., and the hydrogenated block copolymer Tan δ peak (Tg2) observed when 30% by mass of (a) is added to a specific homopolypropylene (propylene unit content of 99% or more and MFR (230 ° C., conforming to ISO 1133) = 1 to 10 g / 10 min) The difference ΔTg (Tg1−Tg2) is preferably in the range of 3 to 12 ° C.
From the same viewpoint, the above (Tg1-Tg2) is preferably 4 to 10 ° C, and more preferably 5 to 9 ° C.
Said (Tg1), (Tg2), and (DELTA) Tg can be measured by the method described in the Example mentioned later.
The ΔTg can be controlled by the ratio of the polymer blocks (B1) and (B2).

The Shore A hardness of the hydrogenated block copolymer (a) is preferably in the range of 15-60. When Shore A hardness is 15-60, the improvement effect of the initial adhesiveness of an adhesive film is acquired.
The range of Shore A hardness is more preferably 25 to 55, and further preferably 30 to 50.
The Shore A hardness of the hydrogenated block copolymer (a) is a polymer block mainly composed of a conjugated diene compound having a vinyl bond content of 1 to 25 mol% before hydrogenation and a polymer mainly composed of a vinyl aromatic compound. It is necessary to have a block, to adjust the content of these polymer blocks, to use a vinyl compound such as a polar compound, Lewis base, ether, amine, etc. It can be controlled by adjusting the rate.
Here, the Shore A hardness can be measured by the method described in Examples described later.

The weight average molecular weight (Mw) (hereinafter also referred to as “Mw”) of the hydrogenated block copolymer (a) is determined from the viewpoint of low blocking property and low hysteresis loss of the hydrogenated block copolymer (a). From the viewpoints of initial tackiness, payout property, low tackiness, and balance of physical properties of the tacky film of the embodiment, it is preferably 100,000 to 300,000, more preferably 130,000 to 270,000. More preferably, it is 150,000 to 250,000.
Mw of the hydrogenated block copolymer (a) can be controlled by the amount of the polymerization initiator.

The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is a calibration curve obtained by measuring the molecular weight of the chromatogram peak obtained by measurement by GPC from the measurement of commercially available standard polystyrene (the peak molecular weight of standard polystyrene is The weight average molecular weight (Mw) determined based on
Specifically, it can measure by the method described in the Example mentioned later.
Similarly, the molecular weight distribution of the hydrogenated block copolymer can be obtained from the measurement by GPC, and the molecular weight distribution is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

  The molecular weight distribution of a single peak measured by gel permeation chromatography (hereinafter also referred to as “GPC”) of the hydrogenated block copolymer (a) is preferably 1.30 or less, more preferably 1 .20 or less, more preferably 1.15 or less, and even more preferably 1.10 or less.

When the above-mentioned hydrogenated block copolymer (a) or the Soxhlet extract dry sample of the adhesive film of this embodiment was measured by 13C-NMR, the integrated value of 29.4-30.0 ppm and 9.0-14 The ratio to the integrated value of 0.0 ppm (integrated value of 29.4 to 30.0 ppm / integrated value of 9.0 to 14.0 ppm) is calculated from the ratio of the integrated value obtained by the following expression (1) (2 It is preferable that the amount of butylene is 50 to 80 mol%.
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)
By setting it as the said range, the characteristic balance of the initial stage adhesiveness of a pressure-sensitive adhesive film obtained, extending | stretching property, and low adhesive progress can be made favorable.
From the same viewpoint, the amount of butylene is preferably 52 to 76 mol%, more preferably 55 to 70 mol%.
Further, in the formula representing the ratio of the integral values, it is preferably in the range of the following formula (3) to the following formula (4), more preferably in the range of the following formula (5) to the following formula (6). .
Ratio of integral values = ((1.84 + ((100-butylene content x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene content ÷ 4) (3)
Ratio of integral values = ((11.05 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (4)
Ratio of integral values = ((2.46 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (5)
Ratio of integral values = ((9.21 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (6)
The ratio of the integral values can be controlled by adjusting the amounts of the polymer blocks (C), (B1), (B2), and (S) and the amount of butylene to the above ranges.
In addition, the ratio of the integrated value is attributed to the structure of the hydrogenated block copolymer (a). If the measurement conditions are the same, the hydrogenated block copolymer (a) was used as a measurement sample. The integrated value does not change between the case and the case where the adhesive film containing the hydrogenated block copolymer (a) is used as the measurement sample.
The amount of butylene in the hydrogenated block copolymer, and the ratio of the butylene amount to the integral value calculated from the above formulas (1) to (6) (integral value of 29.4 to 30.0 ppm / 9.0 to 14) FIG. 1 shows the relationship with the integration value of .0 ppm.

<Method for Producing Hydrogenated Block Copolymer (a)>
Although it does not specifically limit as a manufacturing method of a hydrogenation block copolymer (a), For example, after polymerizing by using an organic alkali metal compound as a polymerization initiator in an organic solvent and obtaining a block copolymer, hydrogen It can manufacture by performing a chemical reaction.
The mode of polymerization may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, a batch polymerization method is preferred.

The polymerization temperature is generally 0 to 150 ° C., preferably 20 to 120 ° C., more preferably 40 to 100 ° C., and still more preferably 55 to 65 ° C.
The polymerization time varies depending on the intended polymer, but is usually within 24 hours, preferably 0.1 to 10 hours. From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, it is more preferably 0.5 to 3 hours.
The atmosphere of the polymerization system is not particularly limited as long as it is within a range of pressure sufficient to maintain nitrogen and the solvent in a liquid phase.
It is preferred that no impurities that inactivate the polymerization initiator and the living polymer, such as water, oxygen, carbon dioxide, etc., are present in the polymerization system.

  Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane and cyclohexane Alicyclic hydrocarbons such as butane and methylcyclopentane; aromatic hydrocarbons such as benzene, xylene, toluene and ethylbenzene.

As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable. As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, or an organic polylithium compound is used.
Examples of the organic lithium compound include, but are not limited to, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, phenyl lithium, hexamethylene di Examples thereof include lithium, butadienyl lithium, and isopropenyl dilithium.
Among these, n-butyllithium and sec-butyllithium are preferable from the viewpoint of polymerization activity.

  The amount of the organic alkali metal compound that is the polymerization initiator depends on the molecular weight of the target block copolymer, but is generally 0.01 to 0.5 phm (parts by mass per 100 parts by mass of the monomer). The range is preferably 0.03 to 0.3 phm, and more preferably 0.05 to 0.15 phm.

The amount of vinyl bonds in the polymer blocks (B1) and (B2) and the polymer site lock (C) contained in the hydrogenated block copolymer (a) is determined based on the presence of Lewis bases such as ethers and amines. It can be adjusted by using it as an agent.
The amount of the vinylating agent used can be adjusted according to the target vinyl bond amount.
Further, by adding a vinylating agent and a metal alkoxide described later in two or more conditions, polymer blocks having different vinyl bond amounts can be produced in a polymer block mainly composed of a conjugated diene compound. .

  Examples of the vinylating agent include, but are not limited to, ether compounds, ether compounds having two or more oxygen atoms, and tertiary amine compounds.

The tertiary amine compound is not limited to the following, but for example, pyridine, N, N, N ′, N′-tetramethylethylenediamine, tributylamine, tetramethylpropanediamine, 1,2-di Examples include, but are not limited to, piperidinoethane and bis [2- (N, N-dimethylamino) ethyl] ether.
These may be used alone or in combination of two or more.
As the tertiary amine compound, a compound having two amines is preferable. Further, among them, those having a structure exhibiting symmetry within the molecule are more preferable, and N, N, N ′, N′-tetramethylethylenediamine and bis [2- (N, N-dimethylamino) ethyl] ether are preferred. And 1,2-dipiperidinoethane are more preferred.

  In the present embodiment, the hydrogenated block copolymer may be copolymerized in the presence of the above-described vinylating agent, organolithium compound, and alkali metal alkoxide. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M is an alkali metal and R is an alkyl group).

The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoints of high vinyl bond content, narrow molecular weight distribution, high polymerization rate, and high block rate.
The alkali metal alkoxide is not limited to the following, but is preferably a sodium alkoxide, a lithium alkoxide, or a potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Sodium alkoxide and potassium alkoxide having an alkyl group are preferable, and sodium-t-butoxide, sodium-t-pentoxide, potassium-t-butoxide, and potassium-t-pentoxide are more preferable.
Among these, sodium tert-butoxide and sodium tert-pentoxide are more preferable.

In the polymerization step of the hydrogenated block copolymer (a), when polymerization is carried out in the presence of a vinylating agent, an organolithium compound, and an alkali metal alkoxide, the molar ratio of the vinylating agent to the organolithium compound (vinylating agent) / Organic lithium compound) and the molar ratio of the alkali metal alkoxide to the organic lithium compound (alkali metal alkoxide / organic lithium compound) are preferably allowed to coexist in the following molar ratio.
Vinylating agent / organic lithium compound is 0.2 to 3.0.
Alkali metal alkoxide / organic lithium compound is 0.01 to 0.3

  The molar ratio of the vinylating agent / organolithium compound should be 0.2 or more from the viewpoint of a high vinyl bond amount and a high polymerization rate, and less than 3.0 from the viewpoint of obtaining a narrow molecular weight distribution and high hydrogenation activity. preferable. The molar ratio of the alkali metal alkoxide / organic lithium compound is 0.01 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate, and a high block ratio, and is 0 from the viewpoint of obtaining a narrow molecular weight distribution and high hydrogenation activity. .3 or less is preferable. Thereby, the polymerization rate is improved, the vinyl bond amount of the target hydrogenated block copolymer can be increased, the molecular weight distribution can be narrowed, and the block rate tends to be improved.

  In the polymerization step, the molar ratio of the vinylating agent / organolithium compound is preferably 0.8 or more from the viewpoint of a high vinyl bond amount and a high polymerization rate, and from the viewpoint of a narrow molecular weight distribution and high hydrogenation activity, 2.5. The following is preferable, and the range of 1.0 or more and 2.0 or less is more preferable.

  The molar ratio of alkali metal alkoxide / organolithium compound is preferably 0.02 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate and a high block ratio, and 0.2 from the viewpoint of a narrow molecular weight distribution and high hydrogenation activity. The following are preferable, 0.03 or more and 0.1 or less are more preferable, and 0.03 or more and 0.08 or less are more preferable.

  Furthermore, the molar ratio of the alkali metal alkoxide / vinylating agent is preferably 0.010 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate, and a high block ratio, realizes a narrow molecular weight distribution, and has a high hydrogen content. From the viewpoint of obtaining activating activity, it is preferably 0.100 or less, more preferably 0.012 or more and 0.080 or less, further preferably 0.015 or more and 0.06 or less, and further preferably 0.015 or more and 0.05 or less.

A deactivator for the vinylating agent can also be used as a method for producing a block having a different amount of vinyl bonds in a polymer block mainly composed of a conjugated diene compound.
Deactivators include alkyl metal compounds and are selected from alkylaluminums having 1 to 20 carbon atoms per alkyl substituent, zinc and magnesium, and mixtures thereof.

The hydrogenation method for producing the hydrogenated block copolymer (a) is not particularly limited. For example, hydrogen is supplied to the block copolymer obtained above in the presence of a hydrogenation catalyst. By hydrogenation, a hydrogenated block copolymer in which the double bond residue of the conjugated diene compound unit is hydrogenated can be obtained.
The hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, and the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, pressure, temperature, and the like.

By pelletizing the hydrogenated block copolymer (a), pellets of the hydrogenated block copolymer (a) can be produced.
As a method of pelletization, for example, a method in which a hydrogenated block copolymer is extruded in a strand form from a single-screw or twin-screw extruder and cut in water with a rotary blade installed on the front surface of the die part; A method in which the hydrogenated block copolymer is extruded into a strand form from an extruder, water-cooled or air-cooled, and then cut by a strand cutter; For example, a method of cutting a sheet into a strip shape and then cutting the sheet into cubic pellets using a pelletizer may be used.
In addition, the magnitude | size and shape of the pellet molded object of a hydrogenation block copolymer (a) are not specifically limited.

If necessary, the hydrogenated block copolymer (a) can be blended with a pellet blocking inhibitor for the purpose of preventing pellet blocking.
Examples of the pellet blocking inhibitor include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica.
From the viewpoints of initial tackiness, feedability, and low tackiness of the tacky film of this embodiment, calcium stearate, polyethylene, and polypropylene are preferred.
A preferable amount is 500 to 6000 ppm with respect to the hydrogenated block copolymer (a). A more preferable amount is 1000 to 5000 ppm with respect to the hydrogenated block copolymer (a). The pellet blocking inhibitor is preferably blended in a state of adhering to the pellet surface, but may be included to some extent inside the pellet.

<Tackifier>
A tackifier may be contained in the adhesive layer of the adhesive film of the present embodiment.
The tackifier is not particularly limited as long as it is a resin capable of imparting viscosity to the adhesive layer. For example, hydrogenated terpene resin, rosin terpene resin, hydrogenated rosin terpene resin, aromatic modification Known tackifying resins such as hydrogenated terpene resins, coumarone resins, phenolic resins, terpene phenol resins, hydrogenated terpene phenol resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins can be used.
In particular, hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene phenol resins, and terpene phenol resins are preferred.
Only one type of tackifier may be used alone, or two or more types may be used in combination.
As specific examples of the tackifier, those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.) can be used. By using a tackifier, the adhesive force can be improved.
The content of the tackifier in the adhesive layer is preferably 0.5 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 10 to 30% by mass in the adhesive layer.
If the content of the tackifier in the pressure-sensitive adhesive layer is 50% by mass or less, the pressure-sensitive adhesive can be effectively prevented and the amount of adhesive residue at the time of peeling tends to be further reduced, which is preferable. If it is 0.5 mass% or more, moderate adhesive force is obtained.

<Hydrogenated block copolymer (b), hydrogenated block copolymer (c)>
The pressure-sensitive adhesive film of the present embodiment has a structure in which the pressure-sensitive adhesive layer further contains 5 to 95% by mass of a hydrogenated block copolymer (b) and / or a hydrogenated block copolymer (c) described later. Preferably, the composition contains 10 to 90 mass%, more preferably 15 to 85 mass%.
By having the said structure, the adhesive film excellent in more moderate initial stage adhesiveness, low temperature adhesiveness, pay-out property, low adhesive progressability, and its characteristic balance is obtained.

The hydrogenated block copolymer (b) is in the molecule,
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b),
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 95 to 70% by mass,
The content of the polymer block (S1) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 30 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b) is 80 mol% or more.

The hydrogenated block copolymer (c) is in the molecule,
A polymer block (B-2) comprising a conjugated diene compound and a vinyl aromatic compound;
A polymer block (S2) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (c),
The content of the polymer block (B-2) containing the conjugated diene compound and the vinyl aromatic compound is 95 to 70% by mass,
The content of the polymer block (S2) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The hydrogenation rate of the hydrogenated block copolymer (c) is 80 mol% or more.

In addition, in the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c), the definition of “mainly”, conjugated diene compound, each material of vinyl aromatic compound, vinyl bond amount, hydrogenation The rate can be defined and controlled in the same manner as the hydrogenated block copolymer (a) described above.
The hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) can be produced by the same method as the method for producing the hydrogenated block copolymer (a) described above.
That is, using the same monomer, the content of each polymer block, the amount of vinyl bonds, the hydrogenation rate, etc. can be controlled under the same conditions.

<Example of structure of hydrogenated block copolymer (b)>
Examples of the hydrogenated block copolymer (b) described above include those having a structure represented by the following general formula.
(S1- (B-1)) _n ,
S1- (B-1) -S1) _n ,
(B-1)-(S1- (B-1)) _n ,
[((B-1) -S1) _n ] _m -Z,
[(S1- (B-1) _n ] _m- Z,
[((B-1) -S1) _n- (B-1)] _m- Z,
[(S1- (B-1)) _n- S1] _m- Z

In the above general formula, S1 is a polymer block (S1) mainly composed of a vinyl aromatic compound, and (B-1) is a polymer block (B-1) mainly composed of a conjugated diene compound.
The boundary line between the polymer block (S1) and the polymer block (B-1) does not necessarily need to be clearly distinguished.
N is an integer of 1 or more, preferably an integer of 1 to 5.
m is an integer greater than or equal to 2, Preferably it is 2-11, More preferably, it is an integer of 2-8.
Z represents a coupling agent residue.
Here, the coupling residue refers to a plurality of copolymers of a conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon compound monomer unit as a polymer block (S1) -polymer block (S1). Coupling agent used for bonding between the polymer block (B-1) and the polymer block (B-1) or between the polymer block (S1) and the polymer block (B-1) Means later residues.
Examples of the coupling agent include a bifunctional coupling agent and a polyfunctional coupling agent.
Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; methyl benzoate, ethyl benzoate, phenyl benzoate, phthalates, and the like. Examples include acid esters.
Examples of the polyfunctional coupling agent having three or more functional groups include, but are not limited to, polyhydric epoxy compounds such as trihydric or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A silicon halide compound represented by R1 _(4-n) SiX _n (wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 or 4), and halogenated A tin compound is mentioned.
Examples of the silicon halide compound include, but are not limited to, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof.
Examples of tin halide compounds include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.
In the above general formula, the vinyl aromatic compound monomer units in the polymer block (S1) and the polymer block (B-1) may be distributed uniformly or in a tapered shape. When the polymer block (S1) and the polymer block (B-1) are copolymer blocks of vinyl aromatic compound monomer units and conjugated diene compound monomer units, the copolymer blocks In the vinyl aromatic compound monomer unit, a plurality of uniformly distributed portions and / or tapered portions may be present. Furthermore, a plurality of portions having different vinyl aromatic compound monomer unit content may coexist in the copolymer block portion.

<Example of structure of hydrogenated block copolymer (c)>
Examples of the hydrogenated block copolymer (c) described above include those having a structure represented by the following general formula.
(S2- (B-2)) _n ,
(B-2)-(S2- (B-2)) _n ,
[((B-2) -S2) _n ] _m- Z,
[((B-2) -S2) _n- (B-2)] _m- Z,

In the above general formula, (B-2) is a polymer block (B-2) containing a conjugated diene compound and a vinyl aromatic compound, and S2 is a polymer block (S2) mainly composed of a vinyl aromatic compound. .
The boundary line between the polymer block (S2) and the polymer block (B-2) is not necessarily clearly distinguished.
N is an integer of 1 or more, preferably an integer of 1 to 5.
m is an integer greater than or equal to 2, Preferably it is 2-11, More preferably, it is an integer of 2-8.
Z represents a coupling agent residue.
Here, the coupling residue refers to a plurality of copolymers of a conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon compound monomer unit as a polymer block (S2) -polymer block (S2). Of coupling agent used for bonding between polymer block (B-2) and polymer block (B-2) or between polymer block (S2) and polymer block (B-2) Means later residues.
Examples of the coupling agent include a bifunctional coupling agent and a polyfunctional coupling agent.
Examples of the bifunctional group coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; methyl benzoate, ethyl benzoate, phenyl benzoate, phthalates, and the like. And acid esters.
Examples of the polyfunctional coupling agent having three or more functional groups include, but are not limited to, polyhydric epoxy compounds such as trihydric or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A silicon halide compound represented by R1 _(4-n) SiX _n (wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 or 4), and halogenated A tin compound is mentioned.
Examples of the silicon halide compound include, but are not limited to, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof.
Examples of tin halide compounds include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.
In the above general formula, the vinyl aromatic compound monomer units in the polymer block (S2) and the polymer block (B-2) may be distributed uniformly or in a tapered shape. When the polymer block (S2) and the polymer block (B-2) are a copolymer block of a vinyl aromatic compound monomer unit and a conjugated diene compound monomer unit, the copolymer block In the vinyl aromatic compound monomer unit, a plurality of uniformly distributed portions and / or tapered portions may be present. Furthermore, a plurality of portions having different vinyl aromatic compound monomer unit content may coexist in the copolymer block portion.

<Other materials>
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present embodiment is a hydrogenated styrenic elastomer or olefin-based material other than the hydrogenated block copolymers (a), (b) and (c) described above, and a tackifier. Contains other materials such as resins, olefinic elastomers, acrylic copolymers, softeners, antioxidants, light stabilizers, pigments, waxes, thermoplastic resins, natural rubber, synthetic rubber, saturated fatty acid bisamide, etc. Also good.

[Hydrogenated styrene elastomer]
The hydrogenated styrene elastomer is not particularly limited. For example, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene random polymer (SBR), and SBS are saturated by hydrogenation. Styrene-ethylene-butylene-styrene (SEBS) and styrene-ethylene-propylene-styrene (SEPS) are typical hydrogenated styrenic elastomers. Other examples include styrene-ethylene-butylene (SEB) and styrene-ethylene. An elastomer having a structure such as propylene (SEP) or styrene / isobutylene / styrene triblock copolymer (SIBS) may be used.

  Moreover, you may use the reactive elastomer which provided various functional groups to the said hydrogenated styrene-type elastomer. Examples of the functional group include, but are not limited to, a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, and a carboxylic acid ester. Group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, Examples include isothiocyanate group, silicon halide group, alkoxysilicon group, tin halide group, boronic acid group, boron-containing group, boronate group, alkoxytin group, and phenyltin group.

[Olefin resin, olefin elastomer]
Examples of the olefin resin and the olefin elastomer include an α-olefin polymer or copolymer having 2 to 20 carbon atoms, and a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.
For example, ethylene-propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methylpentene copolymer, ethylene / 1-octene copolymer, propylene homopolymer , Propylene-ethylene copolymer, propylene / ethylene / 1-butene copolymer, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 4-methylpentene homopolymer 4-methylpentene / 1-propylene copolymer, 4-methylpentene / 1-butene copolymer, 4-methylpentene / 1-propylene / 1-butene copolymer, propylene / 1-butene copolymer , Ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, and the like.
From the viewpoint of stability of adhesive strength over time, propylene homopolymer, propylene-ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, and polyethylene are preferable.

[Acrylic copolymer]
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of this embodiment may further contain an acrylic copolymer. The acrylic copolymer is not particularly limited, and examples thereof include copolymers of methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, and the like with vinyl acetate, vinyl chloride, styrene, and the like.

[Softener]
The adhesive layer of the adhesive film of this embodiment may further contain a softening agent.
The softener is not particularly limited, and for example, any of mineral oil softener and synthetic resin softener can be used. The mineral oil softener generally includes a mixture of aromatic hydrocarbon, naphthene hydrocarbon and paraffin hydrocarbon.
In addition, paraffinic hydrocarbons with 50% or more carbon atoms in all carbon atoms are called paraffinic oils, and naphthenic hydrocarbons with 30 to 45% carbon atoms are called naphthenic oils. In addition, aromatic oils having 35% or more carbon atoms of aromatic hydrocarbons are called aromatic oils. As the mineral oil softener, paraffin oil which is a softener for rubber is preferable, and as the synthetic resin softener, polybutene, low molecular weight polybutadiene and the like are preferable. By including the softening agent, the adhesiveness tends to be further improved in the adhesive film of this embodiment.

  The content of the softening agent in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present embodiment is the above-described hydrogenated block copolymer (a), from the viewpoint of suppressing bleeding of the softening agent and ensuring practically sufficient adhesive strength. When the total mass of the hydrohydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is 100 parts by mass, it is preferably 0 to 100 parts by mass, more preferably 0.1 to 0.1 parts by mass. 80 parts by mass.

[Antioxidants, light stabilizers, etc.]
You may further add stabilizers, such as antioxidant and a light stabilizer, to the adhesion layer of the adhesive film of this embodiment.

  Examples of the antioxidant include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t, for example. -Butylphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) ) Methyl] -o-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)] Hindered phenol antioxidants such as chlorate; sulfur antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) Examples thereof include phosphorus antioxidants such as phosphite and tris (2,4-di-t-butylphenyl) phosphite.

  Examples of the light stabilizer include, but are not limited to, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl). Benzotriazole ultraviolet absorbers such as benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, and benzophenones such as 2-hydroxy-4-methoxybenzophenone System ultraviolet absorbers or hindered amine light stabilizers.

[Pigments, waxes, thermoplastic resins, natural rubber, synthetic rubber]
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present embodiment can contain various additives as necessary in addition to the above.
Examples of the additive include, but are not limited to, pigments such as bengara and titanium dioxide; waxes such as paraffin wax, microcristan wax, and low molecular weight polyethylene wax; amorphous polyolefin, ethylene-ethyl acrylate copolymer, etc. Polyolefin-based or low-molecular-weight vinyl aromatic thermoplastic resin; natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber Synthetic rubber such as Examples of the synthetic rubber include those described in “Rubber / plastic compounding chemicals” (edited by Rubber Digest Co., Ltd.).

[Saturated fatty acid bisamide]
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of this embodiment can contain a saturated fatty acid bisamide that has an effect of suppressing the pressure-sensitive adhesive progress.
Examples of saturated fatty acid bisamides include, but are not limited to, saturated fatty acid aliphatic bisamides such as ethylene bisstearic acid amide (EBSA), methylene bisstearic acid amide, hexamethylene bisstearic acid amide, and m -Saturated fatty acid aromatic bisamides such as xylylene bisstearic acid amide and N, N'-distearylisophthalic acid amide.
Among the saturated fatty acid aliphatic bisamides, ethylene bis stearamide is more preferable.
Of the saturated fatty acid aromatic bisamides, m-xylylene bisstearic acid amide is more preferred.
These saturated fatty acid bisamides may be used alone or in combination of two or more.
Furthermore, you may mix | blend a styrene-type block phase reinforcing agent with the effect which suppresses adhesion progress. Examples of the styrene block phase reinforcing agent include, but are not limited to, for example, styrene and α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, tert-butylstyrene as monomer units. , Styrene compounds such as p-ethylstyrene and divinylbenzene. These may be used alone or in combination of two or more.

(Method for producing resin material constituting the adhesive layer of the adhesive film)
The resin material constituting the adhesive layer of the adhesive film of this embodiment is, for example, a hydrogenated block copolymer (a), a hydrogenated block copolymer (b), a hydrogenated block copolymer (c), and Other components added as necessary can be produced by a method of dry blending, a method of adjusting by an apparatus used for mixing ordinary polymer substances, or the like.
The mixing apparatus is not particularly limited, and examples thereof include a kneading apparatus such as a Banbury mixer, a lab plast mill, a single-screw extruder, a twin-screw extruder, etc., which can be produced by a melt mixing method using an extruder. From the viewpoints of safety and good kneading properties.
In particular, when a tackifier is blended, the above dry blend method may be used. However, since the tackifier has a strong stickiness and a flake shape, the handling property is poor. You may produce the masterbatch previously kneaded in block copolymer (a), (b), or (c). Although the melting temperature at the time of kneading | mixing can be set suitably, it is in the range of 130-300 degreeC normally, and it is preferable that it is the range of 150-250 degreeC.

The resin material constituting the pressure-sensitive adhesive layer of the present embodiment may be subjected to a foaming treatment in order to achieve lightening, softening, and adhesion improving effects.
Examples of the foaming method include, but are not limited to, a chemical method, a physical method, and use of a thermal expansion type microballoon. Bubbles can be distributed inside the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, a physical foaming agent, or the like, or adding a thermal and thermal expansion type microballoon. Moreover, you may aim at weight reduction, softening, and the improvement of adhesiveness by adding a hollow filler (already inflated balloon).

(Method for producing adhesive film)
The adhesive film of this embodiment comprises an adhesive layer containing a hydrogenated block copolymer (a) on a base film.
Although the manufacturing method of the adhesive film of this embodiment is not specifically limited, For example, the method of applying the solution or melt of the resin material which comprises an adhesion layer on a base film, the method using a film extruder, etc. Is mentioned.
Here, when using a solution or melt of the resin material constituting the adhesive layer, the solution or melt may be used after the composition is formed, or the hydrogenated block copolymer (a) may be hydrogenated as necessary. The block copolymer (b) and the hydrogenated block copolymer (c) may be added to a solution or melt and then mixed.

  In the method of coating the solution of the resin material, although not limited to the following, for example, these are dissolved in a soluble solvent, coated on a base film using a coater, etc., and the solvent is heated and dried, etc. Can be manufactured.

  The method for melting and coating the resin material is not limited to the following, but it can be produced, for example, by applying a molten resin material on a base film using a hot melt coater or the like. In this case, it is preferable to use various base films having a glass transition temperature, melting point or softening point higher than the coating temperature.

  The method using the film extruder is not limited to the following. For example, the components of the adhesive layer containing the resin material and the components such as the thermoplastic resin that can form the base film are mixed in a melt co-extruder. In one flow, that is, by adhering the adhesive layer forming fluid and the base material film forming fluid in the die port to form a single fluid and extruding it, the adhesive layer and the resin film layer are combined. Can be manufactured.

  In the case of the method using a film extruder, the resin material for forming the adhesive layer can be manufactured by dry blending each component for the adhesive layer in advance, and thus is an excellent method for productivity. In addition, when extrusion molding is performed, the surface protection film thus produced tends to be particularly excellent in adhesion and adhesive strength.

  The adhesive film of the present embodiment is temporarily attached to the surface of an optical molded body such as a light guide plate and a prism sheet, a synthetic resin plate, a metal plate, a decorative plywood, a coated coated steel plate, various nameplates, etc. It can be used as a protective film for preventing scratches and dirt during processing, transportation and storage.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples.

In Examples and Comparative Examples, hydrogenated block copolymers were prepared by the method described below, and film performance was compared.
At that time, the characteristics of the hydrogenated block copolymer were measured as follows.

[Method for evaluating hydrogenated block copolymer]
((1) Content of each polymer block constituting the hydrogenated block copolymer)
About 20 mL of the polymer solution sampled at each step of the polymerization process of the block copolymer before hydrogenation is injected into a 100 mL bottle sealed with 0.50 mL of n-propylbenzene and about 20 mL of toluene as an internal standard. A sample was prepared.
This sample was measured by gas chromatography equipped with a backed column carrying Apiezon grease (manufactured by Shimadzu Corporation: GC-14B). From the calibration curve of butadiene monomer and styrene monomer obtained in advance, The amount of residual monomers was determined, it was confirmed that the polymerization rate of butadiene monomer and styrene monomer was 100%, and the content of each polymer block was calculated from the following formula.
The polymerization rate of butadiene was measured under the condition of 90 ° C., and the polymerization rate of styrene was measured under the condition of 90 ° C. (10 minutes hold) to 150 ° C. temperature increase (10 ° C./min).
Content of each block = (total amount of monomers fed in each step) / (total monomer amount) × 100 mass%

((2) Vinyl bond amount before hydrogenation of each polymer block constituting the hydrogenated block copolymer)
The polymer sampled at each step of the polymerization process of the block copolymer before hydrogenation was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method.
Measuring instrument is JNM-LA400 (manufactured by JEOL), deuterated chloroform is used as solvent, sample concentration is 50mg / mL, observation frequency is 400MHz, tetramethylsilane is used as chemical shift standard, pulse delay 2.904sec, scan The number of times was 64, the pulse width was 45 °, and the measurement temperature was 26 ° C.
The amount of vinyl bonds is calculated by calculating the integral value per 1H of each bond mode from the integral values of signals attributed to 1,4-bond and 1,2-bond, and then 1,4-bond and 1,2-bond. And calculated from the ratio.
Moreover, the vinyl bond amount of each block was calculated by calculating the vinyl bond amount for each polymer sampled for each step of the polymerization process of the block copolymer before hydrogenation.

((3) Hydrogenation rate of unsaturated bond based on conjugated diene compound unit of hydrogenated block copolymer)
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated block copolymer after hydrogenation.
The measurement conditions and measurement data processing method were the same as in (2) above.
For the hydrogenation rate, an integrated value of a signal derived from a residual double bond of 4.5 to 5.5 ppm and a signal derived from a hydrogenated conjugated diene was calculated, and the ratio was calculated.

((4) Content of vinyl aromatic compound unit in hydrogenated block copolymer (hereinafter also referred to as “styrene content”))
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) method using the polymer after hydrogenation.
Measuring instrument is JNM-LA400 (manufactured by JEOL), deuterated chloroform is used as solvent, sample concentration is 50mg / mL, observation frequency is 400MHz, tetramethylsilane is used as chemical shift standard, pulse delay 2.904sec, scan The number of times was 64, the pulse width was 45 °, and the measurement temperature was 26 ° C.
The styrene content was calculated using the integrated value of the total styrene aromatic signal at 6.2-7.5 ppm of the spectrum.
Further, the content of the total vinyl aromatic compound was calculated by calculating the content of the vinyl aromatic compound unit for each polymer sampled at each step of the polymerization process of the block copolymer before hydrogenation.

((5) Amount of butylene and / or propylene with respect to a total of 100 mol% of conjugated diene compound units)
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated block copolymer after hydrogenation.
The measurement conditions and the measurement data processing method were the same as in (2) and (3) above.
The butylene content was calculated from the ratio of the integral value of the signal attributed to butylene (hydrogenated 1,2-bond) at 0 to 2.0 ppm of the spectrum.

((6) TGIC measurement elution amount peak half-width of hydrogenated block copolymer)
A hydrogenated block copolymer after hydrogenation, and an extract dried sample obtained by Soxhlet extraction (chloroform solvent 90 ° C. × 8 hr) of the adhesive films obtained in Examples and Comparative Examples were dissolved in orthodichlorobenzene. Thus, the solution sample was injected into a graphite carbon column, and the elution amount (mass%) of the sample and the temperature in the column (° C.) at that time were calculated.
The elution amount at each temperature was determined from the elution temperature-elution amount curve obtained from the value.
First, the column containing the filler is heated to 95 ° C., 0.2 mL of a sample solution in which the hydrogenated block copolymer is dissolved in orthodichlorobenzene is introduced, and the temperature of the column is lowered by 2 ° C./min. The temperature was lowered to -20 ° C.
Thereafter, the column temperature was raised to 165 ° C. at a rate of temperature rise of 2 ° C./min, the mobile phase flow rate was 0.5 mL / min, and the concentration of the sample eluted at each temperature was detected.
And the elution temperature-elution amount curve was measured and the elution amount in each temperature was calculated | required.
Apparatus: High-throughput composition analyzer (manufactured by Polymer Char)
Detector: IR5 type infrared spectrophotometer (manufactured by Polymer Char)
Detection wavelength: concentration sensor CH ₂ v3.42 μm (2920 cm ⁻¹ ), methyl sensor CH ₃ v 3.38 μm (2960 cm ⁻¹ )
Column: Porous graphite carbon column, Hypercarb high temperature compatible type (manufactured by Polymer Char), inner diameter 4.6 mm, length 150 mm, particle diameter 5 μm
・ Mobile phase: orthodichlorobenzene, BHT added ・ Sample concentration: 8 mg / 8 mL
Melting conditions: 150 ° C., 60 minutes (under nitrogen atmosphere)
・ Injection volume: 0.2 mL
・ Temperature drop conditions: 95 ° C. to −20 ° C. (2 ° C./min), flow rate 0.0 mL / min ・ Temperature rise conditions: −20 ° C. to −165 ° C. (2 ° C./min), flow rate 0.5 mL / min From the elution temperature-elution amount curve, the half width of the elution peak in the range of 0 ° C. or higher and 150 ° C. or lower was determined.

((7) DSC measurement)
Each 10 mg of hydrogenated block copolymer is precisely weighed in an aluminum pan, and a nitrogen atmosphere (flow rate is 50 mL / min) using a differential scanning calorimeter (DSC) (manufactured by TA Instruments Inc., Q2000). ), The temperature was raised to 150 ° C. at an initial temperature of −50 ° C. and a heating rate of 10 ° C./min, held at 150 ° C. for 5 minutes, and then cooled to −50 ° C. at 10 ° C./min.
The crystallization peak that appears in the temperature-decreasing process of the drawn DSC curve was defined as the crystallization temperature (° C.), and the amount of heat indicated by the crystallization peak area was defined as the crystallization heat amount (J / g).

((8) Temperature-loss tangent (tan δ) measurement obtained by solid viscoelasticity (1 Hz) of hydrogenated block copolymer)
A temperature-loss tangent (tan δ) spectrum obtained by solid viscoelasticity (1 Hz) was measured by the following method to obtain a peak temperature of tan δ.
A measurement sample is set in the twist type geometry of the device ARES (trade name, manufactured by TA Instruments Inc.), the effective measurement length is 25 mm, the strain is 0.5%, the frequency is 1 Hz, and the measurement range is − The following materials were measured from 100 ° C. to 100 ° C. under conditions of a temperature rising rate of 3 ° C./min.
Sample 1: A hydrogenated block copolymer (a) was molded into a sheet having a thickness of 2 mm, and then cut into a size of 10 mm in width and 35 mm in length to obtain a tan δ peak (Tg1) indicating a glass transition as a measurement sample. Asked.
Sample 2: A composition of hydrogenated block copolymer (a) / homopolypropylene (product of Sun Allomer, PL500A) = 30/70 was formed into a sheet having a thickness of 2 mm, and then cut into a size of 10 mm in width and 35 mm in length. As a measurement sample, the low-temperature tan δ peak (Tg2) was determined.
The value of ΔTg (Tg1-Tg2) was determined from Sample 1 and Sample 2.

((9) Shore A hardness of hydrogenated block copolymer)
The shore A hardness (according to ASTM D-2240) of the hydrogenated block copolymer is compression-molded with the hydrogenated block copolymer to produce a sheet having a thickness of 2 mm. The instantaneous value was measured.

((10) Weight average molecular weight of hydrogenated block copolymer)
The weight average molecular weight of the hydrogenated block copolymer was measured by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-10), column: TSKgelGMHXL (4.6 mm ID × 30 cm, 2), solvent: tetrahydrofuran (THF) Was obtained as a polystyrene-equivalent molecular weight by commercially available standard polystyrene.

((11) Microphase separation structure of hydrogenated block copolymer)
The hydrogenated block copolymer pellets obtained in the examples and comparative examples were hot-press molded at 200 ° C. and a 2 mm thick sheet was frozen in liquid nitrogen, and then an ultrathin piece was microtomized in the direction perpendicular to the MD direction. The polymer block (S) phase was cut out, dyed with osmic acid, washed with water, dried, and then observed with a transmission electron microscope (TEM) at a magnification of 50,000 times.
Using image analysis software (A image-kun, manufactured by Asahi Kasei Engineering Co., Ltd.), the morphology of the microphase-separated structure of the block copolymer (S) dyed black present in the TEM image, and the major axis and minor axis The average value was calculated, and the average particle diameter was calculated as the average value of the major axis and the minor axis.
○: The polymer block (S) forms a microphase separation, and has a spherical structure (sphere structure) having an average particle diameter of 5 to 20 nm.
X: The polymer block (S) forms a microphase separation structure other than the above “◯”. Alternatively, a microphase separation structure is not formed.
FIG. 2 shows a TEM image when the evaluation is “◯”, and FIG. 3 shows a TEM image when the evaluation is “x”.

((12) 13C-NMR measurement, calculation of the ratio between the integrated value of 29.4 to 30.0 ppm and the integrated value of 9.0 to 14.0 ppm)
Extracted dry sample obtained by Soxhlet extraction (chloroform solvent 90 ° C. × 8 hr) of the hydrogenated block copolymer and the adhesive films obtained in Examples and Comparative Examples is deuterated chloroform to a concentration of 10 wt / vol%. 13C-NMR of the solution sample was measured under the following conditions, and the ratio of the integrated value of 29.4 to 30.0 ppm and the integrated value of 9.0 to 14.0 ppm (29.4 to 30.0 ppm) Integral value / 9.0-14.0 ppm integral value).
・ Device: Bruker Biospin Avance 600
・ Sample tube: 5mmΦ
・ Chemical shift standard of 0ppm: TMS
-Observation nucleus: 13C
・ Observation frequency: 150.91 MHz
・ Pulse program: zigg30 (quantitative measurement method)
・ Pulse width: 30 °
・ Wait time: 10 sec
-Number of integrations: 5000 times Further, the ratio of each integrated value was calculated by the following formulas (1) and (2).
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)

[Adhesive properties of film]
((1) Initial adhesion (23 ° C))
A universal tensile compression tester “Technograph TGE-500N: manufactured by Minebea Co., Ltd.” was used as an apparatus for measuring the adhesive strength of the adhesive films obtained in Examples and Comparative Examples.
At a temperature of 23 ° C x 50% relative humidity, a 25 mm wide adhesive film cut out is attached to a PMMA plate (arithmetic surface roughness: 0.1 µm) and a 2 kg weight rubber roll (diameter 10 cm) is rolled. The peel strength was measured at a peeling speed of 300 mm / min.
The evaluation was conducted by a 180 ° peeling test in a temperature of 23 ° C. × 50% relative humidity. The initial adhesiveness was evaluated according to the following criteria using the initial adhesive strength.
○: Adhesive strength of 200 g / 25 mm or more Δ: Adhesive strength of 100 g / 25 mm or more to less than 200 g / 25 mm ×: Adhesive strength of less than 100 g / 25 mm

((2) Low temperature tack)
A universal tensile compression tester “Technograph TGE-500N: manufactured by Minebea Co., Ltd.” was used as an apparatus for measuring the adhesive strength of the adhesive films obtained in Examples and Comparative Examples.
At a temperature of 23 ° C x 50% relative humidity, a 25 mm wide adhesive film cut out is attached to a PMMA plate (arithmetic surface roughness: 0.1 µm) and a 2 kg weight rubber roll (diameter 10 cm) is rolled. And pasted.
The samples were left at 23 ° C. and 4 ° C. for 24 hours, and then peeled off at 180 ° with a peeling rate of 300 mm / min in each environment of 23 ° C. and 4 ° C., and the peel strength was measured.
About low temperature adhesiveness, it evaluated by the following reference | standard using the adhesive strength of 23 degreeC and 4 degreeC.
○: Adhesive strength (4 ° C.) is 80% or more of adhesive strength (23 ° C.) Δ: Adhesive strength (4 ° C.) is 50% or more to less than 80% of adhesive strength (23 ° C.) ×: Adhesive strength (4 ° C) is less than 50% of adhesive strength (23 ° C)

((3) Extendability)
The adhesive films obtained in Examples and Comparative Examples were wound up in a form in which an outer layer (paper tube) and an adhesive layer (adhesive film) were in contact with a 3-inch paper tube, attached to a feeding machine, and fed out at 5 m / min. At this time, it was visually confirmed whether or not it could be smoothly fed out without wrinkles or sagging. Evaluation was made according to the following criteria.
○: Can be fed out smoothly △: Can be fed out smoothly even though wrinkles and sagging are present ×: Cannot be drawn out smoothly

((4) Adhesive progress)
A universal tensile compression tester “Technograph TGE-500N: manufactured by Minebea Co., Ltd.” was used as an apparatus for measuring the adhesive strength of the adhesive films obtained in Examples and Comparative Examples.
At a temperature of 23 ° C. and 50% relative humidity, the adhesive film is cut into a width of 25 mm, this is attached to a PMMA plate (surface arithmetic average roughness: 0.1 μm), and a rubber roll (diameter 10 cm) with a weight of 2 kg is rolled. And pasted for 30 minutes.
Thereafter, a 180 ° peel test was performed at a peel rate of 300 mm / min, and the peel strength (initial adhesive strength) was measured.
On the other hand, after sticking the produced adhesive film on a PMMA board by the said method, it heated at 80 degreeC * 1 hour in the gear oven, the adhesion promotion was carried out, and it was left to stand in the measurement environment for 30 minutes. Then, the adhesive strength (adhesive strength after heating acceleration) was measured.
Adhesive progress was evaluated by the following criteria for changes over time in the adhesive strength of the adhesive film before and after heating.
○: Adhesive strength after heating up to 2.0 times the initial adhesive strength Δ: Adhesive strength after heating up to 2.5 times the initial adhesive strength ×: 2.5 times the initial adhesive strength Higher adhesive strength after accelerated heating

[Raw materials]
The hydrogenated block copolymers used in Examples and Comparative Examples were as follows.
(Production Examples 1-7, Comparative Production Examples 1-10)
<Preparation of hydrogenation catalyst>
The hydrogenation catalyst used for the hydrogenation reaction of the hydrogenated block copolymer was prepared by the following method.
Charge 1 L of dried and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride, and add n-hexane solution containing 200 mmol of trimethylaluminum while stirring sufficiently. The reaction was allowed to proceed at room temperature for about 3 days.

(Hydrogenated block copolymer (a))
<Production Example 1: Hydrogenated block copolymer (a-1)>
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a tank reactor with a jacket. 1 L of cyclohexane is put in the reactor, and then n-butyllithium (hereinafter also referred to as “Bu-Li”) is 0.045 parts by mass with respect to 100 parts by mass of all monomers, and N, N as a vinylating agent. , N ′, N′-tetramethylethylenediamine (hereinafter also referred to as “TMEDA”) was added in an amount of 0.05 mol with respect to 1 mol of Bu-Li.
As a first step, a cyclohexane solution containing 10 parts by mass of butadiene (butadiene concentration of 20% by mass) was added over 10 minutes, and then further polymerized for 10 minutes. During the first step polymerization, the temperature was controlled at 65 ° C.
In the second step, TMEDA was added in an amount of 0.45 mol with respect to 1 mol of Bu-Li, a cyclohexane solution containing 34 parts by mass of butadiene (butadiene concentration of 20% by mass) was added over 30 minutes, and then polymerization was performed for another 10 minutes. . The temperature was controlled at 65 ° C. during the second step polymerization.
As a third step, TMEDA was added at 1.10 mol with respect to 1 mol of Bu-Li and sodium t-pentoxide (hereinafter also referred to as “NaOAm”) at 0.05 mol with respect to 1 mol of Bu-Li, and butadiene was added. A cyclohexane solution containing 51 parts by mass (butadiene concentration of 20% by mass) was charged over 30 minutes, and then further polymerized for 10 minutes. The temperature was controlled at 60 ° C. during the third step polymerization.
As a fourth step, a cyclohexane solution (styrene concentration 20% by mass) containing 5 parts by mass of styrene was added over 10 minutes, and then polymerization was further performed for 10 minutes. During the polymerization of the fourth step, the temperature was controlled at 65 ° C.
The polymer was sampled at every step in the polymerization process of the block copolymer.
To the obtained block copolymer, the above hydrogenation catalyst is added so that the concentration in terms of titanium is 100 ppm per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. went. Then, methanol was added, and then 0.25 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.
The hydrogenated block copolymer (a-1) obtained had a hydrogenation rate of 99%, MFR of 2.5 g / 10 min, weight average molecular weight (Mw) 260,000, molecular weight distribution (Mw / Mn). 08.

<Production Example 2: Hydrogenated block copolymer (a-2)>
In the second step, 32 parts by weight of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. In the third step, 48 parts by weight of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. As a step, 7 parts by mass of styrene was charged over 10 minutes and then polymerized for another 10 minutes, and as a fifth step, 3 parts by mass of butadiene was charged over 5 minutes and then polymerized for another 10 minutes ( In the same manner as in a-1), a hydrogenated block copolymer (a-2) was produced.
The obtained hydrogenated block copolymer (a-2) had a hydrogenation rate of 99%, an MFR of 3.5 g / 10 min, a weight average molecular weight (Mw) of 264,000, and a molecular weight distribution of 1.09.

<Production Example 3: Hydrogenated block copolymer (a-3)>
As a first step, 15 parts by mass of butadiene is charged over 10 minutes and then polymerized for another 10 minutes. In a second step, 31 parts by mass of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. In the step, 47 parts by mass of butadiene was added over 30 minutes and then polymerized for another 10 minutes, and as the fourth step, 7 parts by mass of styrene was added over 10 minutes and then polymerized for another 10 minutes ( A hydrogenated block copolymer (a-3) was produced in the same manner as in a-1).
The obtained hydrogenated block copolymer (a-3) had a hydrogenation rate of 99%, MFR 2.3 g / 10 min, weight average molecular weight (Mw) 261,000, and molecular weight distribution 1.08.

<Production Example 4: Hydrogenated block copolymer (a-4)>
Before the first step, Bu-Li is added in an amount of 0.071 parts by mass with respect to 100 parts by mass of all monomers, and as the first step, 3 parts by mass of butadiene is added over 10 minutes, and then further polymerized for 10 minutes. In 2 steps, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. As a fourth step, 12 parts by mass of styrene was added over 10 minutes, and then polymerized for 10 minutes, in the same manner as in (a-1), the hydrogenated block copolymer (a-4) was prepared. Manufactured.
The obtained hydrogenated block copolymer (a-4) had a hydrogenation rate of 99%, an MFR of 2.3 g / 10 min, a weight average molecular weight (Mw) of 167,000, and a molecular weight distribution of 1.09.

<Production Example 5: Hydrogenated block copolymer (a-5)>
As a first step, 5 parts by weight of butadiene is charged over 10 minutes, and then polymerized for another 10 minutes. In a second step, 13.5 parts by weight of butadiene is charged over 15 minutes, and then polymerized for another 10 minutes. (A-1) except that in the third step, TMEDA was added at 0.90 mole per 1 mole of Bu-Li, 76.5 parts by weight of butadiene was added over 45 minutes, and then polymerized for another 10 minutes. In the same manner as above, a hydrogenated block copolymer (a-5) was produced.
The obtained hydrogenated block copolymer (a-5) had a hydrogenation rate of 99%, MFR 4.3 g / 10 min, weight average molecular weight (Mw) 265,000, and molecular weight distribution 1.09.

<Production Example 6: Hydrogenated block copolymer (a-6)>
Before the first step, Bu-Li is added in an amount of 0.047 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 5 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, TMEDA is added in an amount of 0.55 mol with respect to 1 mol of Bu-Li, and 55 parts by mass of butadiene is added over 30 minutes, followed by polymerization for 10 minutes. In the third step, TMEDA is added in 1 mol of Bu-Li. 1.00 mol of butadiene is added, and 37 parts by mass of butadiene is added over 30 minutes, and then further polymerized for 10 minutes. As a fourth step, 3 parts by mass of styrene is added over 10 minutes, and then for another 10 minutes. A hydrogenated block copolymer (a-6) was produced in the same manner as (a-1) except that the polymerization was performed.
The obtained hydrogenated block copolymer (a-6) had a hydrogenation rate of 99%, an MFR of 2.8 g / 10 minutes, a weight average molecular weight (Mw) of 250,000, and a molecular weight distribution of 1.07.

<Production Example 7: Hydrogenated block copolymer (a-7)>
As a first step, 5 parts by mass of butadiene is charged over 10 minutes, and then polymerized for another 10 minutes. In the second step, 0.40 mol of TMEDA is added to 1 mol of Bu-Li, and 45 parts by mass of butadiene are added. Charged over 30 minutes, then polymerized for another 10 minutes. In the third step, except that 45 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, the same as (a-1). A hydrogenated block copolymer (a-7) was produced.
The obtained hydrogenated block copolymer (a-7) had a hydrogenation rate of 99%, an MFR of 1.8 g / 10 min, a weight average molecular weight (Mw) of 262,000, and a molecular weight distribution of 1.07.

<Comparative Production Example 1: Hydrogenated block copolymer (a-8)>
Without performing the first step, in the second step, 38 parts by mass of butadiene was charged over 30 minutes, and then polymerized for another 10 minutes, and in the third step, 57 parts by mass of butadiene was charged over 30 minutes, and then further A hydrogenated block copolymer (a-8) was produced in the same manner as (a-1) except that the polymerization was performed for 10 minutes.
The obtained hydrogenated block copolymer (a-8) had a hydrogenation rate of 99%, MFR of 18.6 g / 10 min, a weight average molecular weight (Mw) of 253,000, and a molecular weight distribution of 1.07.

<Comparative Production Example 2: Hydrogenated block copolymer (a-9)>
Before the first step, Bu4Li was added in an amount of 0.054 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 25 parts by mass of butadiene was added over 10 minutes, and then polymerized for another 5 minutes. In 2 steps, 35 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 35 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, In the same manner as (a-1), a hydrogenated block copolymer (a-9) was produced.
The obtained hydrogenated block copolymer (a-9) had a hydrogenation rate of 99%, an MFR of 1.1 g / 10 min, a weight average molecular weight (Mw) of 226,000, and a molecular weight distribution of 1.08.

<Comparative Production Example 3: Hydrogenated block copolymer (a-10)>
Before the first step, Bu-Li is added in an amount of 0.105 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 15 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, 30 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. In 3rd step, 30 parts by mass of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. As above, a hydrogenated block copolymer (a-10) was produced in the same manner as (a-1) except that 25 parts by mass of styrene was charged over 15 minutes and then polymerized for another 10 minutes.
The obtained hydrogenated block copolymer (a-10) had a hydrogenation rate of 99%, an MFR of 3.1 g / 10 minutes, a weight average molecular weight (Mw) of 100,000, and a molecular weight distribution of 1.09.

<Comparative Production Example 4: Hydrogenated block copolymer (a-11)>
Before the first step, Bu-Li is added in an amount of 0.040 parts by mass with respect to 100 parts by mass of the total monomers. As the first step, 15 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, 34 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 50.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. As 4 steps, hydrogenated block copolymer (a-11) was prepared in the same manner as in (a-1) except that 0.5 part by weight of styrene was charged over 5 minutes and then further polymerized for 5 minutes. Manufactured.
The obtained hydrogenated block copolymer (a-11) had a hydrogenation rate of 99%, MFR of 25.5 g / 10 minutes, a weight average molecular weight (Mw) of 308,000 and a molecular weight distribution of 1.07.

<Comparative Production Example 5: Hydrogenated block copolymer (a-12)>
Before the first step, Bu-Li is added in an amount of 0.050 part by mass with respect to 100 parts by mass of all monomers. As the first step, 5 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. Without performing two steps, in the third step, 1.60 mol of TMEDA was added to 1 mol of Bu-Li, 90 parts by mass of butadiene was added over 60 minutes, and then polymerized for another 10 minutes. As described above, a hydrogenated block copolymer (a-12) was produced in the same manner as (a-1) except that 5 parts by mass of styrene was charged over 10 minutes and then further polymerized for 10 minutes. The obtained hydrogenated block copolymer (a-12) had a hydrogenation rate of 99%, MFR of 3.2 g / 10 min, a weight average molecular weight (Mw) of 241,000, and a molecular weight distribution of 1.06.

<Comparative Production Example 6: Hydrogenated block copolymer (a-13)>
Before the first step, Bu-Li was added in an amount of 0.064 parts by mass with respect to 100 parts by mass of all monomers, and as the first step, 17 parts by mass of butadiene was added over 10 minutes, and then polymerized for another 5 minutes. In 2 steps, TMEDA was added in an amount of 0.30 mol to 1 mol of Bu-Li, 62 parts by mass of butadiene was added over 45 minutes, and then polymerized for another 10 minutes. In the third step, TMEDA was added in 1 mol of Bu-Li. The hydrogenated block copolymer (a) was added in the same manner as (a-1) except that 1.25 mol of butadiene was added, 16 parts by mass of butadiene was added over 15 minutes, and then further polymerized for 10 minutes. -13) was produced.
The obtained hydrogenated block copolymer (a-13) had a hydrogenation rate of 99%, an MFR of 1.2 g / 10 min, a weight average molecular weight (Mw) of 189,000, and a molecular weight distribution of 1.08.

<Comparative Production Example 7: Hydrogenated block copolymer (a-14)>
In the first step, 0.35 mol of TMEDA is added to 1 mol of Bu-Li, and in the second step, 0.15 mol of TMEDA is added to 1 mol of Bu-Li, and 42.5 parts by mass of butadiene is added to 30 parts. It was charged over a period of 10 minutes, and then polymerized for another 10 minutes. In the third step, 42.5 parts by mass of butadiene was charged over 30 minutes and then polymerized for another 10 minutes. Thus, a hydrogenated block copolymer (a-14) was produced.
The obtained hydrogenated block copolymer (a-14) had a hydrogenation rate of 99%, an MFR of 11.8 g / 10 min, a weight average molecular weight (Mw) of 258,000, and a molecular weight distribution of 1.06.

<Comparative Production Example 8: Hydrogenated block copolymer (a-15)>
As a first step, 15 parts by mass of butadiene is charged over 10 minutes and then polymerized for another 5 minutes. In the second step, 0.60 mol of TMEDA is added to 1 mol of Bu-Li, and 50 parts by mass of butadiene are added. Charged for 30 minutes, and then polymerized for another 10 minutes. In the third step, 0.75 mol of TMEDA was added to 1 mol of Bu-Li, and 30 parts by mass of butadiene was charged for 30 minutes, and then further 10 A hydrogenated block copolymer (a-15) was produced in the same manner as (a-1) except that the polymerization was performed for a minute.
The obtained hydrogenated block copolymer (a-15) had a hydrogenation rate of 99%, MFR of 3.2 g / 10 min, a weight average molecular weight (Mw) of 262,000, and a molecular weight distribution of 1.09.

<Comparative Production Example 9: Hydrogenated block copolymer (a-16)>
Before the first step, Bu-Li is added in an amount of 0.064 parts by mass with respect to 100 parts by mass of the total monomers, and in the second step, TMEDA is added in an amount of 0.40 mol with respect to 1 mol of Bu-Li, Into the third step, 0.15 mol of TMEDA is added to 1 mol of Bu-Li and 42.5 parts by mass of butadiene are added over 30 minutes. Then, a hydrogenated block copolymer (a-16) was produced in the same manner as (a-1) except that the polymerization was further continued for 10 minutes.
The obtained hydrogenated block copolymer (a-16) had a hydrogenation rate of 99%, an MFR of 2.0 g / 10 min, a weight average molecular weight (Mw) of 184,000, and a molecular weight distribution of 1.05.

<Comparative Production Example 10: Hydrogenated block copolymer (a-17)>
In the second step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. In the third step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. Then, a hydrogenated block copolymer (a-17) was produced in the same manner as (a-1) except that the subsequent hydrogenation reaction was interrupted.
The obtained hydrogenated block copolymer (a-17) had a hydrogenation rate of 60%, an MFR of 38.8 g / 10 min, a weight average molecular weight (Mw) of 265,000, and a molecular weight distribution of 1.05.

(Hydrogenated block copolymer (b))
<Production Example 8: Hydrogenated block copolymer (b)>
Prior to the first step, 0.070 parts by mass of Bu-Li with respect to 100 parts by mass of all monomers and 1.8 mol of TMEDA with respect to 1 mol of Bu-Li were added. Was added for 5 minutes, and then polymerized for another 10 minutes (the temperature was controlled at 70 ° C. during the polymerization), and in the second step, 8.3 parts by mass of styrene was charged for 10 minutes, and then further 10 Polymerize for 1 minute (the temperature was controlled at 70 ° C. during the polymerization), and in the third step, 80.5 parts by mass of butadiene was added over 60 minutes, and then polymerize for another 10 minutes (the temperature was controlled at 70 ° C. during the polymerization). In the fourth step, 6.7 parts by mass of styrene was charged over 10 minutes, and then further polymerized for 10 minutes (during polymerization, the temperature was controlled at 70 ° C). Was) except that, in the same manner as in Production Example 1 to produce hydrogenated block copolymer of Preparation 8 (b).
The obtained hydrogenated block copolymer (b) of Production Example 8 had a hydrogenation rate of 98%, MFR 7.2 g / 10 min, weight average molecular weight (Mw) 167,000, and molecular weight distribution 1.08.

(Hydrogenated block copolymer (c))
<Production Example 9: Hydrogenated block copolymer (c-1)>
Before the first step, 0.050 parts by mass of Bu-Li with respect to 100 parts by mass of all monomers and 0.4 mol of TMEDA with respect to 1 mol of Bu-Li were added. In the first step, 5 parts by mass of styrene was added. Charged for 10 minutes, and then polymerized for another 10 minutes (temperature was controlled at 70 ° C. during polymerization). In the second step, 42 parts by mass of styrene and 48 parts by mass of butadiene were continuously added at a constant rate over 60 minutes. And then polymerize for another 10 minutes (during polymerization, the temperature was controlled at 70 ° C.), and in the third step, 5 parts by mass of styrene was charged over 10 minutes, and then polymerized for another 10 minutes (during polymerization, temperature The hydrogenated block copolymer (c-1) of Production Example 9 was produced in the same manner as in Production Example 1, except that the temperature was controlled at 70 ° C.
The obtained hydrogenated block copolymer (c-1) of Production Example 9 had a hydrogenation rate of 98%, MFR 4.8 g / 10 min, weight average molecular weight (Mw) 163,000, and molecular weight distribution 1.08. It was.

<Production Example 10: Hydrogenated block copolymer (c-2)>
Prior to the first step, 0.085 parts by mass of Bu-Li with respect to 100 parts by mass of all monomers and 0.7 mol of TMEDA with respect to 1 mol of Bu-Li were added. In the first step, 10 parts by mass of styrene were added. Charged for 10 minutes, then polymerized for another 10 minutes (temperature was controlled at 70 ° C. during polymerization). In the second step, 57 parts by mass of styrene and 33 parts by mass of butadiene were continuously added at a constant rate over 60 minutes. And then polymerize for another 10 minutes (the temperature was controlled at 70 ° C. during the polymerization), and then 0.5 mol of ethyl benzoate was added to 1 mol of Bu-Li, reacted for 10 minutes, and coupled. A hydrogenated block copolymer (c-2) of Production Example 10 was produced in the same manner as Production Example 1 except that the reaction was performed (reaction temperature was controlled at 70 ° C). It was.
The obtained hydrogenated block copolymer (c-2) of Production Example 10 has a hydrogenation rate of 98%, MFR 6.1 g / 10 min, and the ratio of the polymer before and after coupling is 95 by weight average molecular weight (Mw). The polymer having a weight average molecular weight (Mw) of 190,000 was 53% by mass.

[Examples 1-7], [Comparative Examples 1-10]
<Adhesive film-like molded product>
The above-mentioned hydrogenated block copolymer constituting the pressure-sensitive adhesive layer and polypropylene constituting the base material layer (trade name “PC684S” manufactured by Sun Allomer Co., Ltd.), MFR (230 ° C., 2.16 kg load) = 7.5 g / 10 minutes And the two layers were integrated and co-extruded by a T-die type co-extrusion method to produce an adhesive film having a base layer thickness of 40 μm and an adhesive layer thickness of 10 μm.
The initial stage mentioned above using the adhesive film which comprises the adhesive layer which consists of hydrogenated block copolymer (a-1)-(a-17) obtained in Examples 1-7 and Comparative Examples 1-10. Evaluation of adhesiveness, low-temperature adhesiveness, pay-out property, and adhesive progress was performed.

  From the results of Table 3, the adhesive film-like molded bodies obtained in Examples 1 to 7 are practically good in any of low temperature tack, initial adhesiveness, pay-out property, and adhesive advanceability, and have a characteristic balance. It was found to be good.

[Examples 8 to 18], [Comparative Examples 11 and 12]
<Adhesive film-like molded product>
The above hydrogenated block copolymer constituting the adhesive layer and the following tackifier are dry blended in the proportions shown in Table 4 below, and 180 ° C., 75 to 150 rpm with a twin screw extruder (L / D = 42, 32 mmΦ). The mixture was melt-kneaded under the conditions described above to produce pellets for use in the adhesive layer.
This and the polypropylene constituting the base material layer (manufactured by Sun Allomer, trade name “PC684S”, MFR (230 ° C., 2.16 kg load) = 7.5 g / 10 min) are supplied to the extruder, and the T-die method Both layers were integrated and coextruded by a coextrusion method to produce an adhesive film having a base layer thickness of 40 μm and an adhesive layer thickness of 10 μm.
Using the pressure-sensitive adhesive films having the pressure-sensitive adhesive layers obtained in Examples 8 to 18 and Comparative Examples 11 to 12, the above-described initial pressure-sensitive adhesiveness, low-temperature pressure-sensitive adhesiveness, feeding property, and pressure-sensitive adhesive progress were evaluated.

Tackifier-1: Clearon P125 (hydrogenated terpene resin / Yasuhara Chemical Co., Ltd.)
Tackifier-2: YS Polystar G150 (terpene phenol resin / Yasuhara Chemical Co., Ltd.)
Tackifier-3: Clearon M (Aromatic modified terpene resin / Yasuhara Chemical Co., Ltd.)
Tackifier-4: YS Polystar UH (hydrogenated terpene phenol resin / manufactured by Yasuhara Chemical Co., Ltd.)

  From the results of Table 4, the adhesive film-like molded bodies obtained in Examples 8 to 18 are practically good in terms of low-temperature tack, initial adhesiveness, pay-out property, and adhesive progress, and have a good property balance. It turns out that.

  The adhesive film of the present embodiment is temporarily attached to the surface of an optical molded body such as a light guide plate and a prism sheet, a synthetic resin plate, a metal plate, a decorative plywood, a coated coated steel plate, various nameplates, etc. It has industrial applicability as a protective film for preventing scratches and dirt during processing, transportation and storage.

Claims (12)

On the base film,
An adhesive film comprising an adhesive layer comprising a hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) is in the molecule,
A polymer block (C) mainly composed of a conjugated diene compound;
A polymer block (B) mainly composed of a conjugated diene compound;
A polymer block (S) mainly composed of an aromatic vinyl compound;
Including,
The polymer block (B) includes polymer blocks (B1) and (B2),
In the hydrogenated block copolymer (a), the content of the polymer block (C) is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, The content of the polymer block (S) is 1 to 15% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C) is 1 to 25 mol%, the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less, The vinyl bond amount before hydrogenation of the combined block (B2) is more than 60 mol% and 100 mol% or less,
The hydrogenation rate is 80 mol% or more,
Adhesive film. In 100 mass% of the hydrogenated block copolymer (a), the total content of the polymer block (C) and the polymer block (S) is 3 to 27 mass%.
The adhesive film according to claim 1. The content of the polymer block (B1) in 100% by mass of the polymer block copolymer (a) is 10 to 60% by mass, and the content of the polymer block (B2) is 30 to 80% by mass. %
The adhesive film according to claim 1 or 2. On the base film,
An adhesive film comprising an adhesive layer comprising a hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) contains an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule,
The content of the aromatic vinyl compound unit of the hydrogenated block copolymer (a) is 1 to 15% by mass,
The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more,
The amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units in the hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) has a crystallization peak at −20 to 80 ° C., and the crystallization heat quantity is 0.1 to 10 J / g,
The elution amount peak of the hydrogenated block copolymer (a) measured by thermal gradient interaction chromatography (TGIC) is in the range of 0 ° C. or higher and 150 ° C. or lower,
The half-value width of the elution peak is in the range of 20 to 40 ° C.
The hydrogenated block copolymer (a) has a Shore A hardness of 15 to 60,
Adhesive film. Tan δ showing the glass transition of the hydrogenated block copolymer (a) observed in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (1 Hz) of the hydrogenated block copolymer (a) The peak (Tg1) is in the range of more than −45 ° C. and not more than −30 ° C., and the tan δ peak observed when 30% by mass of the hydrogenated block copolymer (a) is added to homopolypropylene ( The difference ΔTg (Tg1−Tg2) from Tg2) is 3 to 12 ° C.,
The adhesive film as described in any one of Claims 1 thru | or 4. Ratio of integrated value of 29.4 to 30.0 ppm measured by 13C-NMR and integrated value of 9.0 to 14.0 ppm (integrated value of 29.4 to 30.0 ppm / 9.0 to 14.0 ppm) Integration value)
It is in the range of the integral value obtained by the following equation (2) from the ratio of the integral value obtained by the following equation (1),
The amount of butylene is 50 to 80 mol%,
The adhesive film as described in any one of Claims 1 thru | or 5.
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2) The adhesive layer further comprises 5 to 95% by mass of a hydrogenated block copolymer (b) and / or a hydrogenated block copolymer (c),
The hydrogenated block copolymer (b) is in the molecule,
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b),
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 95 to 70% by mass,
The content of the polymer block (S1) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 30 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b) is 80 mol% or more,
The hydrogenated block copolymer (c) is in the molecule,
A polymer block (B-2) comprising a conjugated diene compound and a vinyl aromatic compound;
A polymer block (S2) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (c),
The content of the polymer block (B-2) containing the conjugated diene compound and the vinyl aromatic compound is 95 to 70% by mass,
The content of the polymer block (S2) mainly composed of the vinyl aromatic compound is 5 to 30% by mass,
The hydrogenation rate of the hydrogenated block copolymer (c) is 80 mol% or more,
The adhesive film as described in any one of Claims 1 thru | or 6. The adhesive layer is
The adhesive film as described in any one of Claims 1 thru | or 7 containing 0.5-50 mass% of tackifiers. The tackifier is
The pressure-sensitive adhesive film according to claim 8, which is at least one selected from the group consisting of hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene phenol resins, and terpene phenol resins. The polymer block (B) further includes a polymer block (B3) present at the terminal of the hydrogenated block copolymer (a),
The content of the polymer block (B3) is 1 to 10% by mass in the hydrogenated block copolymer (a).
The adhesive film as described in any one of Claims 1 thru | or 9. The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is 100,000 to 300,000.
The adhesive film as described in any one of Claims 1 thru | or 10.   The pressure-sensitive adhesive film according to any one of claims 1 to 11, wherein the microphase separation structure of the hydrogenated block copolymer (a) forms a spherical structure (sphere structure).