Material for pressure-sensitive adhesive, method for producing pressure-sensitive adhesive, pressure-sensitive adhesive, multilayer film, and package

Abstract

To provide a material for a pressure-sensitive adhesive capable forming a pressure-sensitive adhesive layer having high adhesive strength and excellent film appearance.SOLUTION: There is provided a material for a pressure-sensitive adhesive comprising a composition C which comprises at least one thermoplastic elastomer A and is in a particulate form, at least one thermoplastic elastomer D, at least one tackifier E and a composition F in a particulate form where these are integrated, where the mass ratio of the whole tackifier to the whole thermoplastic elastomer of the composition F is more than 1.5 and 3.0 or less and the ratio of the MFR value of the composition F to the MFR value of the composition C is 10 or more and 100 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a material for a pressure-sensitive adhesive, a method for producing a pressure-sensitive adhesive, a pressure-sensitive adhesive, a multilayer film, and a package. [Background technology]

[0002] In recent years, packaging materials that exhibit resealability by using multilayer films containing pressure-sensitive adhesive layers have been proposed, which has led to an increased demand for extrusion-moldable pressure-sensitive adhesives. Generally, a method using a hot melt for pressure-sensitive adhesive is known as a method for forming a pressure-sensitive adhesive layer (see, for example, Patent Document 1). However, the pressure-sensitive adhesive layer disclosed in Patent Document 1 has room for improvement in terms of handling and adhesive strength. In addition, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive material, a method for forming a pressure-sensitive adhesive, a pressure-sensitive adhesive, a multilayer film, and a package have been disclosed that are resistant to blocking, easy to handle, and capable of exhibiting high adhesive strength (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2015-529715 [Patent Document 2] International Publication No. 2019 / 031354 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 2 discloses a method for forming an adhesive layer with relatively high adhesive strength by combining two types of particulate compositions with relatively low adhesive strength and extruding them together using an extruder. However, depending on the conditions for extruding the two types of particulate compositions described in Patent Document 2, the two types of particles may not be well mixed, resulting in insufficient adhesive force being developed, or unmelted particles remaining in the adhesive layer, which may deteriorate the appearance of the film including the adhesive layer.

[0005] Therefore, an object of the present invention is to provide a pressure-sensitive adhesive material, a method for producing a pressure-sensitive adhesive, a pressure-sensitive adhesive, a multilayer film, and a package that can develop sufficient adhesive force under a wide range of extrusion conditions and can form a pressure-sensitive adhesive layer with good film appearance.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that in a pressure-sensitive adhesive material containing a thermoplastic elastomer A and a particulate composition C, and a composition F in which a thermoplastic elastomer D and a tackifier E are integrated, the mass ratio of the total tackifier to the total thermoplastic elastomer in the composition F is within a predetermined numerical range. Let the ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the pressure-sensitive adhesive material be x (total thermoplastic elastomer / total thermoplastic elastomer + total tackifier), the ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the composition C be α, and the ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the composition F be β. When the adhesive force of the pressure-sensitive adhesive material with the ratio x is greater than the adhesive force of the composition C with the ratio α and greater than the adhesive force of the composition F with the ratio β, β < x < α, and the ratio of the MFR of the composition F to the composition C is within a predetermined numerical range, it has been found that the problems of the above prior art can be solved, and the present invention has been completed. That is, the present invention is as follows.

[0007] [1] Pressure-sensitive adhesive materials used in pressure-sensitive adhesives contained in multilayer films for resealable packaging And, At least one thermoplastic elastomer A and at least one tackifier B; Including, These are integrated Composition C, in particulate form; at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains the thermoplastic elastomer A has a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, and contains a block copolymer (C) having one polymer block (A), the content of the block copolymer (C) in the thermoplastic elastomer A being 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D has a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, and contains a block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition F satisfies the following condition (2): The mass ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the pressure-sensitive adhesive material (total thermoplastic elastomer / total thermoplastic elastomer) Let x be the total amount of tackifier (including the total amount of tackifier). The total amount of the thermoplastic elastomer and the tackifier in the composition C is Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + (total tackifier) ​​is α, In the composition F, the total amount of the thermoplastic elastomer and the total amount of the tackifier is Thermoplastic elastomer mass ratio (total thermoplastic elastomer / total thermoplastic elastomer + total When β is the tackifier, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is the same as that of the composition C having the ratio α. Greater than the wearing force, The adhesive strength is greater than that of composition F in which the ratio is β, The following formula (1), and the below described Condition(13) , the following condition (5), the following condition (6) Meet death, the ratio of the amount of composition C to the amount of composition F (composition mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β <x<α (1) <Condition (2)> The mass ratio of the total tackifier to the total thermoplastic elastomer in the composition F is 1.5 is greater than or equal to 3.0. <Condition (13)> the ratio of the MFR value of the composition F to the MFR value of the composition C is 10 or more and 100 or less is. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is 0.4 or more and 2.5 or less. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is 0.6 or more and 1.4 or less. [2] The composition C further contains a tackifier B and satisfies the following condition (1): The pressure-sensitive adhesive material according to [1] above. <Condition (1)> The mass ratio of the total thermoplastic elastomer to the total tackifier in the composition C is 1.5 is greater than or equal to 3.0. [3] Pressure-sensitive adhesive materials used in pressure-sensitive adhesives contained in multilayer films for resealable packaging And, At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains the thermoplastic elastomer A has a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, and contains a block copolymer (C) having one polymer block (A), the content of the block copolymer (C) in the thermoplastic elastomer A being 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D has a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, and contains a block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition C satisfies the following condition (1): The composition F satisfies the following condition (2): The total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive material is The mass ratio of the total thermoplastic elastomer to the total thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer) Let x be the total amount of tackifier (including the total amount of tackifier). The total amount of the thermoplastic elastomer and the tackifier in the composition C is Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + (total tackifier) ​​is α, In the composition F, the total amount of the thermoplastic elastomer and the total amount of the tackifier is Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + When the total tackifier is β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is the same as that of the composition C having the ratio α. and the adhesive strength is greater than that of composition F in which the ratio is β, The following formula (1) , the following condition (5), the following condition (6) Meet death, the ratio of the amount of composition C to the amount of composition F (composition mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β <x<α (1) <Condition (1)> The mass ratio of the total thermoplastic elastomer to the total tackifier in the composition C is 1.5 is greater than or equal to 3.0. <Condition (2)> The mass ratio of the total tackifier to the total thermoplastic elastomer in the composition F is 1.5 is greater than or equal to 3.0. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is 0.4 or more and 2.5 or less. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is 0.6 or more and 1.4 or less. [4] Pressure-sensitive adhesive materials used in pressure-sensitive adhesives contained in multilayer films for resealable packaging And, At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains the thermoplastic elastomer A has a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, and contains a block copolymer (C) having one polymer block (A), the content of the block copolymer (C) in the thermoplastic elastomer A being 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D has a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, and contains a block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition C satisfies the following condition (3): The composition F satisfies the following condition (4): In the material for pressure-sensitive adhesives, of total thermoplastic elastomer relative to the total amount of all thermoplastic elastomers and all tackifiers Let the mass ratio (total thermoplastic elastomer / total thermoplastic elastomer + total tackifier) ​​be x. , relative to the total amount of all thermoplastic elastomers and all tackifiers in the composition C, Mass ratio of total thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer) + total tackifier) ​​is α, In the composition F, relative to the total amount of all thermoplastic elastomers and all tackifiers, Mass ratio of total thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer) + total tackifier) ​​is β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is the same as that of the composition C having the ratio α. and the adhesive strength is greater than that of composition F in which the ratio is β, The following formula (1) , the following condition (5), the following condition (6) Meet death, the ratio of the amount of composition C to the amount of composition F (composition mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β <x<α (1) <Condition (3)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition C is More than 60% by mass and less than 80% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition C is More than 20% by mass and less than 40% by mass. <Condition (4)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition F is More than 20% by mass and less than 40% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition F is More than 60% by mass and less than 80% by mass. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is 0.4 or more and 2.5 or less. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is 0.6 or more and 1.4 or less. [5] The tackifier B and the tackifier E are A hydrogenated hydrocarbon resin and / or its derivative having a softening point of 130°C or less. The pressure-sensitive adhesive material according to any one of [1] to [4] above. [6] The tackifier B or the tackifier E is A hydrogenated aromatic petroleum hydrocarbon resin (C9 resin) and / or its derivative, The pressure-sensitive adhesive material according to any one of [1] to [4] above. [7] The tackifier B or the tackifier E is Hydrogenated aromatic modified alicyclic hydrocarbon resin (DCPD-C9 resin) and / or its It is a derivative The pressure-sensitive adhesive material according to any one of [1] to [4] above. [8] The tackifier B is a hydrogenated product of an aromatic petroleum hydrocarbon resin (C9 resin) and / or Its derivative, The tackifier E is a hydrogen bond of an aromatic modified alicyclic hydrocarbon resin (DCPD-C9 resin). additives and / or their derivatives, The pressure-sensitive adhesive material according to any one of [1] to [4] above. 〔9〕 At least one thermoplastic elastomer A and at least one tackifier B Composition C, which is in particulate form and contains At least one thermoplastic elastomer D and at least one tackifier E Composition F, which is in particulate form and contains The material for pressure-sensitive adhesives according to any one of [1] to [4] above, which contains an extrusion step of extruding the mixture through an extruder to obtain a pressure-sensitive adhesive; 1. A method for producing a pressure-sensitive adhesive contained in a multilayer resealable packaging film, comprising: The composition C satisfies the following condition (7): The composition F satisfies the following condition (8): In the extrusion step, of the total amount of the thermoplastic elastomer and the tackifier in the pressure-sensitive adhesive. Mass ratio of total thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer) + total tackifier) ​​is y, In the composition C, the total amount of the thermoplastic elastomer and the tackifier is Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + total tackifier) ​​is α, In the composition F, the total amount of the thermoplastic elastomer and the tackifier is Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + total When β is the tackifier, The adhesive strength of the pressure-sensitive adhesive having a ratio of y is greater than that of composition C having a ratio of α. The adhesive strength is greater than that of composition F, which has a ratio of β. Satisfying the following formula (2): A method for producing a pressure-sensitive adhesive. β <y<α (2) <Condition (7)> The mass ratio of the total thermoplastic elastomer to the total tackifier in the composition C is 1.5 is greater than or equal to 3.0. <Condition (8)> The mass ratio of the total tackifier to the total thermoplastic elastomer in the composition F is 1.5 is greater than or equal to 3.0. 〔10〕 At least one thermoplastic elastomer A and at least one tackifier B Composition C, which is in particulate form and contains At least one thermoplastic elastomer D and at least one tackifier E Composition F, which is in particulate form and contains The material for pressure-sensitive adhesives according to any one of [1] to [4] above, which contains an extrusion step of extruding the mixture through an extruder to obtain a pressure-sensitive adhesive; 1. A method for producing a pressure-sensitive adhesive contained in a multilayer resealable packaging film, comprising: The composition C satisfies the following condition (9): The composition F satisfies the following condition (10): In the extrusion step, The total amount of the thermoplastic elastomer and the tackifier in the pressure-sensitive adhesive Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + The total tackifier is y, In the composition C, the ratio of the total amount of the thermoplastic elastomer to the total amount of the tackifier Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + total thermoplastic elastomer) Adhesion imparting agent) is α, In the composition F, the ratio of the total amount of the thermoplastic elastomer to the total amount of the tackifier Mass ratio of thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer + total thermoplastic elastomer) When the adhesive agent is β, The adhesive strength of the pressure-sensitive adhesive having a ratio of y is greater than the adhesive strength of composition C having a ratio of α; The adhesive strength is greater than that of composition F, whose ratio is β, Satisfying the following formula (2): A method for producing a pressure-sensitive adhesive. β <y<α (2) <Condition (9)> The ratio of the mass of the total thermoplastic elastomer to the total mass of the composition C is 60 mass% and less than 80% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition C is more than 20 mass% and less than 40 mass%. It is less than % by mass. <Condition (10)> The ratio of the mass of the total thermoplastic elastomer to the total mass of the composition F is 20 mass% and less than 40% by mass, The ratio of the mass of all tackifiers to the total mass of the composition F is more than 60 mass% and less than 80 mass%. It is less than % by mass. 〔11〕 The composition C and the composition F, A dry blending step of dry-blending the compositions to prepare a material G for a pressure-sensitive adhesive is included prior to the extrusion step. The aforementioned [9] or

[10] A method for producing the pressure-sensitive adhesive described in 〔12〕 [1] to 〔8〕 A pressure-sensitive adhesive comprising the material for a pressure-sensitive adhesive according to any one of the above items. 〔13〕 The aforementioned 〔12〕 A multilayer film comprising the pressure-sensitive adhesive described in . 〔14〕 The aforementioned 〔13〕 A packaging body comprising the multilayer film according to claim 1. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a pressure-sensitive adhesive material, a method for producing a pressure-sensitive adhesive, a pressure-sensitive adhesive, and a multilayer film and package using the same, which are capable of forming a pressure-sensitive adhesive layer that exhibits sufficient adhesive strength over a wide range of extrusion conditions and results in a good film appearance. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. It should be noted that the following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content, and the present invention can be implemented in various modified forms within the scope of its gist.

[0010] The material for a pressure-sensitive adhesive of this embodiment includes materials for a pressure-sensitive adhesive of the following first to third embodiments, which are collectively referred to herein as the material for a pressure-sensitive adhesive of this embodiment. (First embodiment) The pressure-sensitive adhesive material of the first embodiment is a pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, a composition C comprising at least one thermoplastic elastomer A and in particulate form; at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains The composition F satisfies the following condition (2): The mass ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the pressure-sensitive adhesive material. (Total thermoplastic elastomers / Total thermoplastic elastomers + Total tackifiers) is x, In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, When the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the composition F (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the material for a pressure-sensitive adhesive in which the ratio is x is greater than the adhesive strength of composition C in which the ratio is α, The adhesive strength is greater than that of composition F in which the ratio is β, The material for a pressure-sensitive adhesive satisfies the following formula (1) and condition (13). β <x<α (1) <Condition (2)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less. <Condition (13)> The ratio of the MFR value of the composition F to the MFR value of the composition C is 10 or more and 100 or less.

[0011] In the first embodiment, the composition C may contain a tackifier. In the case where the composition C further contains a tackifier B, it is preferable that the composition C satisfies the following condition (1). <Condition (1)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and 3.0 or less.

[0012] (Second embodiment) The pressure-sensitive adhesive material of the second embodiment is a pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains The composition C satisfies the following condition (1): The composition F satisfies the following condition (2): The mass ratio of the total thermoplastic elastomer to the total amount of the total thermoplastic elastomer and the total tackifier in the pressure-sensitive adhesive material. (Total thermoplastic elastomers / Total thermoplastic elastomers + Total tackifiers) is x, In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, When the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the composition F (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the material for a pressure-sensitive adhesive in which the ratio is x is greater than the adhesive strength of composition C in which the ratio is α, The adhesive strength is greater than that of composition F in which the ratio is β, The material for pressure-sensitive adhesive satisfies the following formula (1): β <x<α (1) <Condition (1)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and 3.0 or less. <Condition (2)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less.

[0013] (Third embodiment) The pressure-sensitive adhesive material of the third embodiment is a pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: at least one thermoplastic elastomer D and at least one tackifier E; Composition F, which comprises: Contains The composition C satisfies the following condition (3): The composition F satisfies the following condition (4): In the pressure-sensitive adhesive material, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as x; In the composition C, relative to the total amount of all thermoplastic elastomers and all tackifiers, The mass ratio of the total thermoplastic elastomers (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is defined as α, In the composition F, relative to the total amount of all thermoplastic elastomers and all tackifiers, When the mass ratio of all thermoplastic elastomers (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is greater than the adhesive strength of composition C having the ratio α and greater than the adhesive strength of composition F having the ratio β; The material for pressure-sensitive adhesive satisfies the following formula (1): β <x<α (1) <Condition (3)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition C is More than 60% by mass and less than 80% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition C is More than 20% by mass and less than 40% by mass. <Condition (4)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition F is More than 20% by mass and less than 40% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition F is More than 60% by mass and less than 80% by mass.

[0014] In the material for pressure-sensitive adhesives of the first embodiment, composition F satisfies <condition (2)> and composition C satisfies <condition (1)>, and in the material for pressure-sensitive adhesives of the second embodiment, composition C satisfies <condition (1)> and composition F satisfies <condition (2)>, thereby weakening the adhesive strength and making it less susceptible to blocking and easier to handle. Furthermore, by using composition C and composition F in combination, the composition ratio of the thermoplastic elastomer and the tackifier in the mixture can be optimized as a pressure-sensitive adhesive, excellent pressure-sensitive adhesive strength can be exhibited, and the two can be melt-mixed under a wide range of operating conditions of the extruder. In other words, by using the pressure-sensitive adhesive material of this embodiment in combination with Compositions C and F, which have different ratios of tackifier and thermoplastic elastomer, the material can be melt-mixed even under conditions that are not favorable for homogenizing molded bodies of different compositions, such as low temperature and short time, and therefore it is possible to form a relatively homogeneous layer of pressure-sensitive adhesive that can exhibit the desired adhesive strength, even without strict control of the extrusion conditions of the extruder.

[0015] In this specification, the term "integrated form" refers to a form that is united as a solid. A form in which a composition containing at least a thermoplastic elastomer and a tackifier is melt-kneaded to form a homogeneous molded body (pellets, beads, etc.) is one of the preferred integrated forms, but it is not essential that the molded body be homogenized, and each component may be fused together as a single unit.

[0016] In the <Condition (2)> of the first embodiment and the <Condition (2)> of the second embodiment, the mass ratio of all tackifiers to all thermoplastic elastomers in composition F is greater than 1.5 and not greater than 3.0. In composition F, the lower limit of (mass of total tackifiers / mass of total thermoplastic elastomers) is preferably greater than 1.6, more preferably greater than 1.7, and even more preferably greater than 1.9. When the lower limit of the mass ratio of all tackifiers to all thermoplastic elastomers is within the above range, the adhesive strength of composition F tends to be weaker, blocking is less likely to occur, and handling becomes easier. Furthermore, the upper limit of the mass ratio of all tackifiers to all thermoplastic elastomers in composition F (mass of all tackifiers / total thermoplastic elastomers) is preferably 2.9 or less, more preferably 2.8 or less, and even more preferably 2.7 or less. By setting the upper limit of the mass ratio of all tackifiers to all thermoplastic elastomers within the above range, the fluidity of the particulate composition increases, becoming similar to that of composition C, and also making it easier to apply an equal force to the two types of particulate compositions when extruded by an extruder. As a result, compositions F and C tend to mix uniformly, which tends to improve the adhesive strength of the pressure-sensitive adhesive formed during extrusion, tends to improve the in-plane uniformity of the adhesive strength, and also tends to reduce unmelted material and improve the appearance of the film.

[0017] In <Condition (1)> of the material for a pressure-sensitive adhesive of the first embodiment and <Condition (1)> of the material for a pressure-sensitive adhesive of the second embodiment, the mass ratio of the total thermoplastic elastomer to the total tackifier in composition C (mass of total thermoplastic elastomer / mass of total tackifier) ​​is greater than 1.5 and not more than 3.0. The lower limit of (mass of total thermoplastic elastomers / mass of total tackifiers) is preferably greater than 1.8, more preferably greater than 2.0, and even more preferably greater than 2.2. When the lower limit of the mass ratio of the total thermoplastic elastomer to the total tackifier is within the above range, the adhesive strength of composition C tends to be weaker, blocking is less likely to occur, and handling becomes easier. Furthermore, the upper limit of the mass ratio of all thermoplastic elastomers to all tackifiers in composition C (mass of all thermoplastic elastomers / mass of all tackifiers) is preferably 2.8 or less, more preferably 2.6 or less, and even more preferably 2.4 or less. By setting the upper limit of the mass ratio of all thermoplastic elastomers to all tackifiers within the above range, the fluidity of particulate composition C increases, becoming similar to that of composition F, and so it becomes easier to apply an even force to the two types of particulate compositions when they are extruded together using an extruder. As a result, composition C tends to mix uniformly with composition F, which tends to improve the adhesive strength of the pressure-sensitive adhesive formed during extrusion, improve the in-plane uniformity of the adhesive strength, reduce unmelted material, and improve the appearance of the film.

[0018] In the pressure-sensitive adhesive material of the third embodiment, in <Condition (3)>, the proportion of the total thermoplastic elastomer in composition C relative to the total mass of composition C is more than 60 mass% and less than 80 mass%, preferably 63 to 77 mass%, more preferably 65 to 75 mass%. In the pressure-sensitive adhesive material of the third embodiment, in <Condition (3)>, the ratio of the mass of all tackifiers to the total mass of composition C is more than 20 mass% and less than 40 mass%, preferably 23 to 37 mass%, more preferably 25 to 35 mass%. When the composition C satisfies the above-mentioned <condition (3)>, the adhesive strength is weakened, so that blocking is less likely to occur and handling becomes easier.

[0019] In the pressure-sensitive adhesive material of the third embodiment, in <Condition (4)>, the proportion of the total thermoplastic elastomer in composition F relative to the total mass of composition F is more than 20 mass% and less than 40 mass%, preferably 23 to 37 mass%, more preferably 25 to 35 mass%. In the pressure-sensitive adhesive material of the third embodiment, in <Condition (4)>, the ratio of the mass of all tackifiers to the total mass of composition F is more than 60 mass% and less than 80 mass%, preferably 63 to 77 mass%, more preferably 65 to 75 mass%. When the composition C satisfies the above-mentioned <condition (4)>, the adhesive strength is weakened, so that blocking is less likely to occur and handling becomes easier.

[0020] In the pressure-sensitive adhesive material of the first embodiment, in <Condition (13)>, the ratio of the MFR value of composition F to the MFR value of composition C is 10 or more and 100 or less. In the pressure-sensitive adhesive composition of this embodiment, composition F satisfies <condition (13)>, so that composition C and composition F tend to be mixed more uniformly while ensuring ease of handling.

[0021] The lower limit of the ratio of the MFR value of composition F to the MFR value of composition C is 10 or more, preferably 15 or more, more preferably 20 or more, and even more preferably 30 or more. When the lower limit of the ratio of the MFR value of the composition F to the MFR value of the composition C is within the above range, the adhesive strength of the pressure-sensitive adhesive formed upon extrusion tends to improve. Moreover, the upper limit of the ratio of the MFR value of the composition F to the MFR value of the composition C is 100 or less, preferably 80 or less, more preferably 70 or less, still more preferably 65 or less, and even more preferably 60 or less. When the upper limit value of the ratio of the MFR value of the composition F to the MFR value of the composition C is within the above range, the fluidities of the compositions C and F can be made closer. By making the time until melting in the extruder and the viscosity during melting closer, it tends to be easier to mix more uniformly. As a result, it tends to be easier to approach an appropriate ratio and the adhesive strength tends to improve. Also, unmelted matter is less likely to remain, and the appearance of the film tends to be improved.

[0022] As a method for achieving the <Condition 13>, the following methods can be mentioned. Any one of these methods may be selected, or two or more of them may be combined. (1) Adjust the ratio of the thermoplastic elastomer and the tackifier in the composition F and the composition C. (2) Design the structures of the thermoplastic elastomers in the composition F and the composition C. (3) Adjust the molecular weights of the thermoplastic elastomers in the composition F and the composition C. (4) Select the tackifiers in the composition F and the composition C.

[0023] In the method of (1), when the composition F and the composition C contain the same thermoplastic elastomer, if only the composition F contains a tackifier, the difference in the MFR values of the composition C and the composition F tends to be large. Also, within the range satisfying the relationship of β < x < α, formula (1), by making the composition C also contain a tackifier, it can be controlled to satisfy the <Condition 13>.

[0024] In the method (1) above, the MFR value may be adjusted by making composition F and composition C contain different thermoplastic elastomers. Possible embodiments in which composition F and composition C contain different thermoplastic elastomers include an embodiment in which the structures of the respective thermoplastic elastomers are different, as in the method (2) above, to adjust the MFR values ​​of the thermoplastic elastomers, and an embodiment in which the molecular weights of the thermoplastic elastomers are different while the structures are common, as in the method (3) above.

[0025] When the molecular weights of the thermoplastic elastomers of Composition C and Composition F are equivalent, the MFR value of the thermoplastic elastomer tends to increase as the content of vinyl aromatic monomer units decreases, the content of vinyl structure monomer units in the conjugated diene monomer increases, the branched structure decreases, and the hydrogenation rate relative to the total amount of unsaturated double bonds derived from the conjugated diene compound decreases.

[0026] When composition F and composition C contain thermoplastic elastomers having equivalent molecular weights but different structures, the above <Condition 13> tends to be more easily achieved when composition C contains a thermoplastic elastomer that has a lower content of vinyl aromatic monomer units, a higher content of vinyl structural monomer units in conjugated diene monomers, fewer branched structures, and a structure with a lower hydrogenation rate relative to the total amount of unsaturated double bonds derived from conjugated diene compounds than composition F.

[0027] The structures of the thermoplastic elastomers contained in Compositions C and F may be set so that the ratio of MFR values ​​satisfies the above-mentioned <Condition (13)>, taking into account the above-mentioned requirements. However, since <Condition (13)> specifies not the MFR value of the thermoplastic elastomer but the MFR values ​​of Compositions C and F, which may contain a tackifier, etc., it is important to note that the MFR values ​​of Compositions C and F as a whole are adjusted, not the MFR value of the thermoplastic elastomer alone. For example, if composition F contains a tackifier with high fluidity, and if composition C does not contain a tackifier, it is preferable to use a thermoplastic elastomer with a higher MFR value for composition C.

[0028] When the molecular structures of the thermoplastic elastomers contained in Composition C and Composition F are the same, the lower the molecular weight of the thermoplastic elastomer, the greater the MFR value of the thermoplastic elastomer tends to be. When composition F and composition C contain thermoplastic elastomers having the same structure but different molecular weights, the above-mentioned <condition (13)> tends to be more easily achieved when composition C contains a thermoplastic elastomer having a lower molecular weight than composition F.

[0029] As described above, the fluidity (MFR value) of Compositions C and F can be controlled by adjusting the structure of the thermoplastic elastomers contained in Compositions C and F. However, from the viewpoint of improving mixability when two types of particulate Compositions C and F are extruded together using an extruder and improving the adhesive strength of the pressure-sensitive adhesive formed upon extrusion, it is preferable that Compositions C and F each contain at least one type of thermoplastic elastomer and at least one type of tackifier.

[0030] Furthermore, by appropriately selecting the tackifier contained in composition C and composition F, it is also possible to control the ratio of the MFR values ​​of composition C and composition F. Tackifiers generally have much higher fluidity than thermoplastic elastomers. Therefore, when only composition F contains a tackifier, selecting a tackifier with a low MFR value tends to more easily satisfy the above-mentioned <condition (13)>.

[0031] Furthermore, the lower the softening point of a tackifier used, the greater the MFR values ​​of Compositions C and F when combined with a thermoplastic elastomer. Tackifiers are often natural products and the like, and their structures are often unspecified or not uniform, so it is difficult to make general statements; however, the softening point of a tackifier is thought to be affected by its molecular weight, and when comparing tackifiers with the same structure, the MFR value tends to be higher when a tackifier with a lower molecular weight and softening point is used. In this way, the fluidity of Compositions C and F can be predicted from the molecular weight and softening point. However, compatibility with the thermoplastic elastomer to be combined varies depending not only on the molecular weight and softening point of the tackifier but also on the structure of the tackifier, and it is believed that the compatibility between the tackifier and the thermoplastic elastomer affects the fluidity of Compositions C and F. For this reason, it is believed that it is difficult to determine the fluidity solely based on the molecular weight and softening point of the tackifier. Therefore, by selecting a tackifier taking into consideration the compatibility between the tackifier and the thermoplastic elastomer in addition to the molecular weight and softening point of the tackifier, it tends to be easier to achieve the above-mentioned <Condition (13)>.

[0032] The fluidity (MFR value) can be controlled by the structure of the tackifier contained in the composition. However, from the viewpoints of improving the mixing ability when the two types of particulate Compositions C and F are extruded together in an extruder, improving the adhesive strength of the pressure-sensitive adhesive formed upon extrusion, and improving the appearance and odor characteristics, it is preferable that Compositions C and F each contain at least one type of thermoplastic elastomer and at least one type of tackifier. From the same viewpoint, it is preferable that the tackifier resin B contained in composition C and the tackifier E contained in composition F are hydrogenated hydrocarbon resins and / or derivatives thereof having a softening point of 130°C or lower.

[0033] In order to satisfy the above-mentioned <Condition (13)>, it is effective to adjust the flowability (MFR value) of composition C and / or composition F. Specifically, when measured according to the melt flow rate (MFR) measurement method described below, the MFR value of composition C is preferably 0.6 g / min or more, more preferably 1.2 g / min or more, even more preferably 1.8 g / min or more, even more preferably 2.4 g / min or more, and even more preferably 3.0 g / min or more. When the MFR value of composition C is within the above range, the fluidity of composition C is close to that of composition F. Therefore, when the two types of particulate composition C and composition F are extruded together using an extruder, force is more likely to be applied evenly to the two types of particulate composition C and composition F, and composition C tends to mix uniformly with composition F. As a result, the adhesive strength of the pressure-sensitive adhesive formed during extrusion tends to improve, the in-plane uniformity of the adhesive strength tends to improve, and unmelted material tends to decrease, tending to improve the appearance of the film.

[0034] Furthermore, the MFR value of composition F, when measured according to the melt flow rate (MFR) measurement method described below, is preferably 400 g / min or less, more preferably 390 g / min or less, even more preferably 380 g / min or less, even more preferably 370 g / min or less, and even more preferably 350 g / min or less. When the MFR value of composition F is within the above range, the fluidity of composition F is close to that of composition C. In addition, when extruded using an extruder, force is more likely to be applied evenly to the two types of particulate composition C and composition F. As a result, compositions C and F tend to mix uniformly, which tends to improve the adhesive strength of the pressure-sensitive adhesive formed during extrusion, improve the in-plane uniformity of the adhesive strength, reduce unmelted material, and improve the appearance of the film.

[0035] Composition C included in the material for a pressure-sensitive adhesive of the first embodiment contains at least one type of thermoplastic elastomer A and has a particulate form. Furthermore, the composition C contained in the material for a pressure-sensitive adhesive of the second and third embodiments contains at least one type of thermoplastic elastomer A and at least one type of tackifier B, and has a particulate form in which these are integrated together. Composition F contained in the pressure-sensitive adhesive material of the first to third embodiments contains at least one type of thermoplastic elastomer D and at least one type of tackifier E, and these have an integrated particulate form.

[0036] The thermoplastic elastomer may be used alone or in combination of two or more kinds. Furthermore, the tackifier may be used alone or in combination of two or more kinds. That is, Compositions C and F may contain various types of thermoplastic elastomers and tackifiers, and are not limited to a form containing only specific thermoplastic elastomers A and D or tackifiers B and E. The composition C may also contain components other than the thermoplastic elastomer A and the tackifier B (hereinafter also referred to as "other components") as appropriate. Furthermore, the composition F may also contain components other than the thermoplastic elastomer D and the tackifier E (hereinafter also referred to as "other components") as appropriate.

[0037] Examples of the other components include a softener. The softener refers to a substance that has the function of lowering the hardness and viscosity of Compositions C and F. Softeners include, but are not limited to, oils; plasticizers; synthetic liquid oligomers; and mixtures thereof. Oils can be suitably used from the viewpoints of reducing the viscosity, improving the adhesion, and reducing the hardness of Compositions C and F. Examples of oils include, but are not limited to, known paraffinic process oils, naphthenic process oils, aromatic process oils, and mixed oils thereof. The softener may be used alone or in combination of two or more kinds. When the pressure-sensitive adhesive material of this embodiment is used for food packaging, from the viewpoint of suppressing transfer of the softener to food due to bleed-out of the softener, the content of the softener is preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably substantially free of the softener, relative to the total of Composition C and Composition F. This "substantially free of the softener" means that the softener is not actively added, but does not exclude even amounts that are unavoidably mixed into production plants, materials, etc.

[0038] Compositions C and F constituting the pressure-sensitive adhesive material of this embodiment are in the form of particles. The term "particulate" as used herein refers to a shape known as a pellet, bead, crumb, dense pellet, or the like, in which the size of each particle is generally uniform. The generally uniform size of each particle prevents classification during extrusion molding, and tends to facilitate the formation of a highly uniform pressure-sensitive adhesive.

[0039] Compositions C and F constituting the pressure-sensitive adhesive material of this embodiment preferably have low adhesive properties, from the viewpoint of being more resistant to blocking and being easy to handle. "Low adhesive performance" means that when a layer made of Composition C or Composition F is formed on a substrate and the adhesive strength is measured according to the "Method for Measuring Adhesion Strength (Thermoplastic Elastomer, Each Composition, and Each Dry Blend Composition)" described below, the adhesive strength is 15.0 N / 10 mm or less. From the same viewpoint, the adhesive strength is preferably 14.0 N / 10 mm or less, more preferably 13.0 N / 10 mm or less, even more preferably 12.0 N / 10 mm or less, even more preferably 10.0 N / 10 mm or less, even more preferably 5.0 N / 10 mm or less, and particularly preferably 1.0 N / 10 mm or less. Furthermore, from the same viewpoint, when the adhesive strength is measured according to the "Method for Measuring Tack Strength" (for the thermoplastic elastomer, each composition, and each dry blend composition) described below, the tack strength is preferably 10.0 N / 5 mmΦ or less, more preferably 8.0 N / 5 mmΦ or less, even more preferably 6.0 N / 5 mmΦ or less, even more preferably 5.0 N / 5 mmΦ or less, even more preferably 3.0 N / 5 mmΦ or less, and particularly preferably 1.0 N / 5 mmΦ or less.

[0040] (Thermoplastic elastomers A and D) Composition C and Composition F contain at least one type of thermoplastic elastomer A and at least one type of thermoplastic elastomer D, respectively. Thermoplastic elastomers A and D are specific thermoplastic elastomers contained in compositions C and F, respectively, but compositions C and F may contain other thermoplastic elastomers.

[0041] First, the thermoplastic elastomer A constituting composition C will be explained below. The thermoplastic elastomer D constituting composition F will be explained later. (Thermoplastic elastomer A) The thermoplastic elastomer A is not particularly limited, but examples thereof include polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polybutadiene-based thermoplastic elastomers. On the other hand, from the viewpoint that strong adhesive strength is likely to be exhibited when Composition C is mixed with Composition F, it is preferable that the thermoplastic elastomer A is a block copolymer containing a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units. The term "vinyl aromatic monomer unit" refers to a structure resulting from the polymerization of one vinyl aromatic hydrocarbon compound, and the term "conjugated diene monomer unit" refers to a structure resulting from the polymerization of one conjugated diene compound.

[0042] Examples of vinyl aromatic hydrocarbon compounds include, but are not limited to, alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-tertiary butylstyrene, alkoxystyrenes such as p-methoxystyrene, vinylnaphthalene, etc. Among these, styrene is preferred as the vinyl aromatic hydrocarbon compound. The vinyl aromatic hydrocarbon compounds may be used alone or in combination of two or more.

[0043] The conjugated diene compound is not particularly limited as long as it is a diolefin having a conjugated double bond, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Among these, 1,3-butadiene and isoprene are preferred as conjugated diene compounds. Furthermore, the use of 1,3-butadiene is particularly preferred because it tends to result in a pressure-sensitive adhesive with excellent heat aging resistance and light resistance. Furthermore, the use of 1,3-butadiene is preferred because it improves heat aging resistance, thereby suppressing deterioration due to heating in the extruder, making it less likely for performance to decrease, and reducing odor. The use of isoprene is preferred because it tends to improve the flexibility of the pressure-sensitive adhesive. The conjugated diene compounds may be used alone or in combination of two or more.

[0044] The "polymer block (A) mainly composed of vinyl aromatic monomer units" refers to a polymer block in which the proportion of vinyl aromatic monomer units relative to the entire polymer block (A) is 50 mass% or more, preferably 70 mass% or more, more preferably 85 mass% or more, and even more preferably 95 mass% or more. Furthermore, the term "polymer block (B) mainly composed of conjugated diene monomer units" refers to a polymer block in which the proportion of conjugated diene monomer units in the entire polymer block (B) exceeds 50% by mass, preferably 70% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more.

[0045] The content of the vinyl aromatic monomer unit in the thermoplastic elastomer A is preferably 10% by mass or more and 40% by mass or less. When the content of the vinyl aromatic monomer unit is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive that is likely to exhibit even better adhesive strength tends to be obtained. Furthermore, from the viewpoint of obtaining a material for a pressure-sensitive adhesive that exhibits even higher holding power, the lower limit of the content is preferably 12% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Furthermore, from the viewpoint of obtaining a material for a pressure-sensitive adhesive that exhibits even higher adhesive power, the upper limit of the content of the vinyl aromatic monomer unit is preferably 35% by mass or less, more preferably 32% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less. The content can be measured by the method described in the examples below.

[0046] From the viewpoint that composition C is likely to exhibit even stronger adhesive strength when mixed with composition F, at least thermoplastic elastomer A contained in composition C preferably contains a block copolymer (C) having a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, and having one polymer block (A). The content of the block copolymer (C) in the thermoplastic elastomer A is preferably 10% by mass or more and 90% by mass or less. When the content of the block copolymer (C) is within the above range, when the composition C is mixed with the composition F, a material for a pressure-sensitive adhesive that is likely to exhibit even better adhesive strength tends to be obtained. Furthermore, from the viewpoint that a material for a pressure-sensitive adhesive that exhibits even higher tack strength can be obtained when composition C is mixed with composition F, the content of block copolymer (C) in the thermoplastic elastomer A is more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and even more preferably 60% by mass or more. Furthermore, from the viewpoint of obtaining a material for a pressure-sensitive adhesive that exhibits even higher holding power, the content of the block copolymer (C) in the thermoplastic elastomer A is more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less.

[0047] The weight-average molecular weight of the block copolymer (C) having one polymer block (A) constituting the thermoplastic elastomer A is preferably 30,000 or more and 200,000 or less. When the weight-average molecular weight of the block copolymer (C) is within the above range, a material for a pressure-sensitive adhesive tends to be obtained that is more likely to exhibit excellent adhesive strength and tackiness than when composition C is mixed with composition F. Furthermore, from the viewpoint of obtaining a pressure-sensitive adhesive material that is more likely to exhibit high softening point characteristics, the weight average molecular weight of the block copolymer (C) is more preferably 40,000 or more, even more preferably 50,000 or more, even more preferably 60,000 or more, even more preferably 70,000 or more, and particularly preferably 80,000 or more. Furthermore, from the viewpoint that a pressure-sensitive adhesive material that is more likely to exhibit even better adhesive strength and tackiness, as well as low melt viscosity characteristics, can be obtained when composition C is mixed with composition F, the weight-average molecular weight of block copolymer (C) is more preferably 180,000 or less, even more preferably 150,000 or less, even more preferably 130,000 or less, and even more preferably 120,000 or less.

[0048] The structure of the block copolymer (C) having one polymer block (A) is not particularly limited, and examples thereof include (AB), (AB)X, (BA)X, (BAB), and (BAB)X (A represents the polymer block (A), B represents the polymer block (B), and X represents a residue of a coupling agent or a residue of a polymerization initiator). Among these, a diblock copolymer represented by formula (AB) or formula (AB)X is preferred. Because the block copolymer (C) has such a structure, when it is mixed with composition C and composition F, it tends to exhibit even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0049] Furthermore, it is preferable that the thermoplastic elastomer A further contains a component having a weight-average molecular weight ratio to the weight-average molecular weight of the block copolymer (C) of 1.5 or more and less than 2.5 (block copolymer (D-1)), i.e., (Mw of block copolymer (D-1) / Mw of block copolymer (C)) = 1.5 or more and less than 2.5). The weight average molecular weight ratio of block copolymer (D-1) / block copolymer (C) is preferably 1.6 or more and less than 2.4, and more preferably 1.7 or more and less than 2.3. When the weight average molecular weight ratio of block copolymer (D-1) / block copolymer (C) is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that is more likely to exhibit even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0050] It is also preferred that the thermoplastic elastomer A further contains a component having a weight-average molecular weight ratio to the weight-average molecular weight of the block copolymer (C) of 2.5 or more and less than 3.4 (block copolymer (D-2)), i.e., (Mw of block copolymer (D-2) / Mw of block copolymer (C)) = 2.5 or more and less than 3.4). The weight-average molecular weight ratio of block copolymer (D-2) / block copolymer (C) is preferably 2.6 or more and less than 3.3, more preferably 2.7 or more and less than 3.2. When the weight-average molecular weight ratio of block copolymer (D-2) / block copolymer (C) is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that is more likely to exhibit even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0051] Furthermore, it is preferable that the thermoplastic elastomer A further contains a component having a weight-average molecular weight ratio to the weight-average molecular weight of the block copolymer (C) of 3.4 or more and less than 4.5 (block copolymer (D-3)), i.e., (Mw of block copolymer (D-3) / Mw of block copolymer (C)) = 3.4 or more and less than 4.5). The weight-average molecular weight ratio of block copolymer (D-3) / block copolymer (C) is preferably 3.5 or more and less than 4.4, more preferably 3.6 or more and less than 4.3. When the weight-average molecular weight ratio of block copolymer (D-3) / block copolymer (C) is within the above range, when composition C is mixed with composition F, it tends to easily exhibit even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0052] The area ratio of the block copolymer (D-1) in the GPC elution curve to the total area (=1) in the GPC elution curve of the thermoplastic elastomer A is preferably 0.00 or more and 0.20 or less, more preferably 0.01 or more and 0.10 or less, and even more preferably 0.02 or more and 0.08 or less. When the area ratio in the GPC elution curve of the block copolymer (D-1) is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that has even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0053] Furthermore, the area ratio of the block copolymer (D-2) in the GPC elution curve to the total area of ​​the thermoplastic elastomer A in the GPC elution curve (=1) is preferably 0.10 or more and 0.50 or less, more preferably 0.12 or more and 0.45 or less, and even more preferably 0.13 or more and 0.4 or less. When the area ratio in the GPC elution curve of the block copolymer (D-2) is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that has even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0054] The area ratio of the block copolymer (D-3) in the GPC elution curve to the total area (=1) of the thermoplastic elastomer A in the GPC elution curve is preferably 0.10 or more and 0.50 or less, more preferably 0.12 or more and 0.45 or less, and even more preferably 0.13 or more and 0.4 or less. When the area ratio in the GPC elution curve of the block copolymer (D-3) is within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that has even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0055] The ratio of the area in the GPC elution curve of the block copolymer (D-2) to the area in the GPC elution curve of the block copolymer (D-1) (block copolymer (D-2) / block copolymer (D-1)) is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. By having the area ratio in the GPC elution curve fall within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that has even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0056] The ratio of the area in the GPC elution curve of block copolymer (D-3) to the area in the GPC elution curve of block copolymer (D-1) (block copolymer (D-3) / block copolymer (D-1)) is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. By having the area ratio in the GPC elution curve fall within the above range, when composition C is mixed with composition F, a material for a pressure-sensitive adhesive tends to be obtained that has even better adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0057] The weight-average molecular weight ratio of block copolymer (D-1), block copolymer (D-2) and block copolymer (D-3) to block copolymer (C), and the area ratio in the GPC elution curve of block copolymer (D-1), block copolymer (D-2) and block copolymer (D-3) can be controlled within the above range by adjusting the coupling reaction conditions, specifically, the type of coupling agent, its addition amount, reaction temperature and reaction time. For example, by selecting a compound containing four functional groups as a coupling agent, the weight-average molecular weight ratio and the area ratio in the GPC elution curve can be controlled.

[0058] The structures of the block copolymer (D-1), the block copolymer (D-2), and the block copolymer (D-3) are not particularly limited, and they may be composed of only a single structure or may be a mixture of structures having multiple types. For example, [(AB) N ] m , [(AB) N ] m X, [(BA) N ] m X, [(AB) N A] m X, [(BA) N B] mX (A represents a polymer block (A) mainly composed of vinyl aromatic monomer units, B represents a polymer block (B) mainly composed of conjugated diene monomer units, X represents a residue of a coupling agent or a residue of a polymerization initiator, N represents 1 to 5, and m represents 2 to 8 (preferably 2 to 6, more preferably 2 to 4)). Among these, the block copolymer (D-1) is preferably a bi-branched block copolymer represented by the formula (AB)2X (hereinafter also referred to as a "bifunctional block copolymer"). The block copolymer (D-2) is preferably a three-branched block copolymer represented by the formula (AB)3X (hereinafter also referred to as a "trifunctional block copolymer"). The block copolymer (D-3) is preferably a tetra-branched block copolymer represented by the formula (AB)4X (hereinafter also referred to as a "tetrafunctional block copolymer"). By containing the three-branched block copolymer and the four-branched block copolymer, when Composition C is mixed with Composition F, a material for a pressure-sensitive adhesive tends to be obtained that is more likely to exhibit excellent adhesive strength, low melt viscosity characteristics, and high softening point characteristics.

[0059] The hydrogenation rate H relative to the total amount of unsaturated double bonds derived from the conjugated diene compound in the polymer block (B) mainly composed of conjugated diene monomer units is preferably 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, and even more preferably 80 mol% or more. When the hydrogenation rate H is within the above range, there is a tendency for even better heat resistance stability to be exhibited. Furthermore, the hydrogenation rate H relative to the total amount of unsaturated double bonds derived from the conjugated diene compound in the polymer block (B) mainly composed of conjugated diene monomer units is preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, still more preferably 65 mol% or less, still more preferably 60 mol% or less, particularly preferably 55 mol% or less, and even more preferably 50 mol% or less. When the hydrogenation rate H is within the above range, a composition C tends to be obtained which has a low Tg and is likely to exhibit excellent adhesive strength at lower temperatures. In addition, compatibility with tackifiers is improved, and there is a tendency for even better adhesive strength to be exhibited. Furthermore, when the material for pressure-sensitive adhesives is mixed more uniformly with composition F and extruded, the in-plane uniformity of the adhesive strength tends to be further improved, and the formation of fisheyes tends to be further suppressed.

[0060] (Tackifiers B and D) Composition C contains at least one type of tackifier B. Tackifier B is a specific tackifier contained in composition C, but composition C may also contain other tackifiers. Composition F also contains at least one type of tackifier E. Tackifier E is a specific tackifier contained in composition F, but composition F may also contain other tackifiers.

[0061] Tackifiers B and D may be in the form of a resin (tackifying resin), and can be selected from a wide variety of types depending on the application and required performance of the resulting pressure-sensitive adhesive material. Examples of tackifiers B and D that are at least contained in Composition C and Composition F include, but are not limited to, rosin-based compounds such as natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin, and pentaerythritol ester of hydrogenated rosin; copolymers of natural terpene, three-dimensional polymers of natural terpene, aromatic modified terpene resins, hydrogenated derivatives of aromatic modified terpene resins, terpene phenolic resins, hydrogenated derivatives of terpene phenolic resins, terpene resins (monoterpene, diterpene, triterpene, polypertene, etc.), and hydrogenated terpene resins. and terpene-based compounds such as hydrogenated derivatives of hydrogenated terpene resins; petroleum hydrocarbon compounds such as aliphatic petroleum hydrocarbon resins (C5-based resins), hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins (C9-based resins), hydrogenated products of aromatic petroleum hydrocarbon resins, derivatives of hydrogenated products of aromatic petroleum hydrocarbon resins, hydrogenated products of aromatic modified alicyclic hydrocarbon resins (DCPD-C9-based resins) and / or derivatives thereof, dicyclopentadiene-based resins, hydrogenated derivatives of dicyclopentadiene-based resins, C5 / C9 copolymer-based resins, hydrogenated products of C5 / C9 copolymer-based resins and derivatives thereof, cycloaliphatic petroleum hydrocarbon resins, hydrogenated products of cycloaliphatic petroleum hydrocarbon resins and derivatives thereof, and aromatic group-containing resins. These tackifiers can be used alone or in combination of two or more. Note that the C5 / C9 copolymer system is a copolymerized petroleum resin polymerized using a mixture of C5 fraction and C9 fraction as a raw material.

[0062] The following will explain in more detail the preferred tackifiers B and D depending on the application and performance. From the viewpoint of suppressing coloration and reducing odor, the tackifiers B and D contained in the compositions C and F are preferably hydrogenated products and derivatives thereof. Examples of hydrogenated products and derivatives thereof include, but are not limited to, hydrogenated products and derivatives of aromatic modified terpene resins, hydrogenated products and derivatives of terpene phenol resins, hydrogenated products and derivatives of hydrogenated terpene resins, hydrogenated products and derivatives of aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated products and derivatives of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products and derivatives of dicyclopentadiene resins, hydrogenated products and derivatives of C5 / C9 copolymer resins, and hydrogenated products and derivatives of cyclic aliphatic petroleum hydrocarbon resins. Among these, hydrogenated products of aromatic petroleum hydrocarbon resins (C9 resins) and derivatives thereof, hydrogenated products of dicyclopentadiene resins and derivatives thereof, hydrogenated products of hydrogenated terpene resins and derivatives thereof, and the like are particularly preferred. Commercially available hydrogenated products and derivatives thereof include, but are not limited to, the Alcon P and M series (trade names) manufactured by Arakawa Chemical Industry Co., Ltd., the Regalite R series manufactured by Eastman Chemical Company, the Imave S and P series manufactured by Idemitsu Kosan Co., Ltd., the Escolez 5000 series (trade names) manufactured by ExxonMobil Chemical Company, the Clearon P series manufactured by Yasuhara Chemical Company, and the Escolez SU400 series manufactured by Kolon.

[0063] Furthermore, from the viewpoint of obtaining a pressure-sensitive adhesive material that is well compatible with the thermoplastic elastomers A and D and exhibits excellent adhesive strength, tackifiers B and E are preferably hydrogenated hydrocarbon resins and / or derivatives thereof that have a softening point of 130°C or lower. The lower limit of the softening point of tackifiers B and E is preferably not less than 90° C., more preferably not less than 93° C., and even more preferably not less than 95° C. When the softening points of tackifiers B and E are within the above range, even better adhesive strength is exhibited. The upper limit of the softening point is preferably less than 128° C., more preferably less than 126° C., and even more preferably less than 125° C. When the softening points of the tackifiers B and E are within the above ranges, even better adhesive strength is exhibited. The softening points of tackifiers B and E can be controlled by adjusting various factors such as the structure, degree of polymerization, and molecular weight of the tackifiers B and E, and may be related to the adhesive strength of the pressure-sensitive adhesive material as well as compatibility with thermoplastic elastomers A and D. It is a preferred embodiment to control the softening point by molecular weight and select the type of resin from the standpoint of color and odor.

[0064] Examples of tackifiers other than the various hydrogenated products and derivatives thereof described above include, but are not limited to, natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin, pentaerythritol ester of hydrogenated rosin; copolymers of natural terpene, three-dimensional polymers of natural terpene, aromatic modified terpene resins, terpene phenol resins, terpene resins, hydrogenated terpene resins; aliphatic petroleum hydrocarbon resins (C5 resins), aromatic petroleum hydrocarbon resins (C9 resins), dicyclopentadiene resins, C5 / C9 copolymer resins, and alicyclic petroleum hydrocarbon resins. Among these, aliphatic petroleum hydrocarbon resins (C5 resins), aromatic petroleum hydrocarbon resins (C9 resins), C5 / C9 copolymer resins, cycloaliphatic petroleum hydrocarbon resins, terpene resins, natural and modified rosin esters, and mixtures thereof are preferred. Commercially available products include aliphatic petroleum hydrocarbon resins (C5 resins), such as the Quinton 100 series (trade name) manufactured by Zeon Corporation, the Escoretz 1000 series manufactured by ExxonMobil Chemical Corporation, and the WING TACK series (trade name) manufactured by Cray Valley; aromatic petroleum hydrocarbon resins (C9 resins), C5 / C9 copolymer resins, such as the PICCOTAC series (trade name) manufactured by Eastman Chemical Company, the Escoretz 2000 series (trade name) manufactured by ExxonMobil Chemical Company, and the FTR series (trade name) manufactured by Mitsui Chemicals, Inc.; and terpene resins and natural and modified rosin esters, such as the SYLVALITE series and SYLVARES series (trade name) manufactured by Arizona Chemical Company, the PICCOLYTE series (trade name) manufactured by PINOVA Corporation, and the YS Resin PX series (trade name) manufactured by Yasuhara Chemical Company.

[0065] From the viewpoint of compatibility with the thermoplastic elastomer A described above, the tackifier B contained in the composition C is preferably at least one selected from the group consisting of aromatic modified terpene resins, terpene phenol resins, terpene resins, aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, dicyclopentadiene resins, C5 / C9 copolymer resins, and hydrogenated derivatives thereof. From the viewpoint of compatibility with the thermoplastic elastomer D described below, the tackifier E contained in composition F is preferably at least one selected from the group consisting of aromatic modified terpene resins, terpene phenol resins, terpene resins, aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, dicyclopentadiene resins, C5 / C9 copolymer resins, and hydrogenated derivatives thereof.

[0066] Furthermore, from the viewpoint of obtaining a pressure-sensitive adhesive material that exhibits even better adhesive strength and high holding power when composition C is mixed with composition F, and from the viewpoint of exhibiting high compatibility with thermoplastic elastomer D and making it easier to obtain a more uniform pressure-sensitive adhesive material when they are simultaneously extruded in an extruder, terpene resins are more preferred as at least tackifier B contained in composition C. There are no particular limitations on the terpene resin, but the YS Resin PX series (trade name) manufactured by Yasuhara Chemical Co., Ltd. can be preferably used.

[0067] When composition C is mixed with composition F, a material for a pressure-sensitive adhesive that is likely to exhibit high adhesive strength and high holding power is obtained, and from the viewpoint of economy, it is preferable that the tackifier B contained in composition C is an aliphatic tackifier. Examples of aliphatic tackifiers include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated aliphatic petroleum hydrocarbon resins (C5 resins) and derivatives thereof, C5 / C9 copolymer resins, and hydrogenated C5 / C9 copolymer resins and derivatives thereof. The aliphatic tackifier refers to a tackifier having an aliphatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 88% by mass or more, and even more preferably 95% by mass or more. By ensuring that the content of aliphatic hydrocarbon groups is within the above range, when Composition C is mixed with Composition F, even better adhesive strength and holding power are likely to be exhibited, and the cost efficiency tends to be even better.

[0068] The aliphatic tackifier can be produced by homopolymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. Monomers having an aliphatic group and a polymerizable unsaturated group include, but are not limited to, natural and synthetic terpenes, for example, containing C5 or C6 cyclopentyl or cyclohexyl groups. Other monomers that can be used in copolymerization include, but are not limited to, 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, and terpene-phenol resins.

[0069] From the viewpoint of obtaining a pressure-sensitive adhesive material having high adhesive strength and high coatability when Composition C is mixed with Composition F, it is preferable that the tackifier B contained in Composition C is at least an aromatic tackifier. The aromatic tackifier is not particularly limited, but examples thereof include aromatic petroleum hydrocarbon resins (C9 resins) and C5 / C9 copolymer resins. The aromatic tackifier refers to a tackifier having an aromatic hydrocarbon group content of preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 88% by mass or more, and still more preferably 95% by mass or more. By ensuring that the content of aromatic hydrocarbon groups is within the above range, when composition C is mixed with composition F, the adhesive strength tends to be further improved.

[0070] The aromatic tackifier can be produced by homopolymerizing or copolymerizing a monomer having an aromatic group and a polymerizable unsaturated group. Examples of monomers each having an aromatic group and a polymerizable unsaturated group include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, methoxystyrene, tert-butylstyrene, chlorostyrene, and indene monomers (including methylindene). Furthermore, other monomers that can be used in copolymerization are not particularly limited, but examples thereof include 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, terpene, and terpene-phenol resins.

[0071] From the viewpoint of obtaining high adhesive strength when composition C is mixed with composition F, and from the viewpoint of suppressing changes in adhesive strength over time or creep performance (the smaller the value, the better), it is more preferable that composition C contains, as at least tackifier B, 20 to 75 mass% of a tackifier that has affinity for the non-glass phase block (usually the middle block) of the block copolymer, and 3 to 30 mass% of a tackifier that has affinity for the glass phase block (usually the outer block) of the block copolymer.

[0072] The tackifier having an affinity for the glass phase block of the block copolymer is not particularly limited, but for example, a resin having an aromatic ring between molecules is preferred. Examples of such resins include, but are not limited to, aromatic group-containing resins such as homopolymers or copolymers containing vinyltoluene, styrene, α-methylstyrene, coumarone, or indene as structural units. Among these, KristAlEx and PlAstolyN (trade names, manufactured by Eastman Chemical Co.) containing α-methylstyrene are preferred.

[0073] The content of the tackifier having affinity for the glass phase block of the block copolymer is preferably 3 to 30 mass %, more preferably 5 to 20 mass %, and even more preferably 6 to 12 mass %, relative to 100 mass % of Composition C.

[0074] From the viewpoints of high initial adhesive strength, high wettability, low melt viscosity, high coatability, etc., petroleum resins with an aromatic content of 3 to 12 mass% are preferred as tackifiers. Examples of such petroleum resins include, but are not limited to, aliphatic petroleum hydrocarbon resins (C5 resins), hydrogenated aliphatic petroleum hydrocarbon resins (C5 resins) and derivatives thereof, aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated aromatic petroleum hydrocarbon resins (C9 resins) and derivatives thereof, dicyclopentadiene resins, hydrogenated dicyclopentadiene resins and derivatives thereof, C5 / C9 copolymer resins, hydrogenated C5 / C9 copolymer resins and derivatives thereof, cycloaliphatic petroleum hydrocarbon resins, and hydrogenated cycloaliphatic petroleum hydrocarbon resins and derivatives thereof. The aroma content of the petroleum resin is preferably 3 to 12 mass %, more preferably 4 to 10 mass %. Among these, hydrogenated petroleum resin is particularly preferred.

[0075] Furthermore, in the pressure-sensitive adhesive material of this embodiment, the tackifier B is preferably a hydrogenated product of an aromatic petroleum hydrocarbon resin (C9 resin) and / or a derivative thereof, from the viewpoints of exhibiting excellent adhesive strength and productivity. By using tackifier B as a hydrogenated product of aromatic petroleum hydrocarbon resin (C9 resin) and / or its derivative, it is possible to prevent multiple particles of composition C from adhering together (for example, two or three pellets becoming connected together), and it becomes possible to produce the composition C in a particulate form. Furthermore, from the viewpoints of excellent adhesive strength, low-temperature properties, and productivity, the tackifier E is preferably a hydrogenated product of an aromatic-modified alicyclic hydrocarbon resin (DCPD-C9 resin) and / or a derivative thereof. Since the tackifier resin E is a hydrogenated product of an aromatic-modified alicyclic hydrocarbon resin (DCPD-C9 resin) and / or a derivative thereof, it becomes possible to produce particles of the composition F in a uniform shape, i.e., in a granular form, without multiple particles adhering together. As described above, by combining tackifier resin B and tackifier resin E, the pressure-sensitive adhesive formed during extrusion tends to have improved peel strength, the in-plane uniformity of peel strength tends to be improved, unmelted material tends to be reduced, and the appearance of the film tends to be improved.

[0076] (Thermoplastic elastomer D) Composition F contains at least one thermoplastic elastomer D. Thermoplastic elastomer D is a specific thermoplastic elastomer contained in composition F, but composition F may contain other thermoplastic elastomers. Thermoplastic elastomer D may be the same as or different from the above-mentioned thermoplastic elastomer A. Here, "the same" means that thermoplastic elastomer D has the same structure as thermoplastic elastomer A. From the viewpoint of further improving compatibility and mixability with thermoplastic elastomer A, it is preferable that thermoplastic elastomer D is the same as thermoplastic elastomer A, and from the viewpoint of making it easier to design a wider range of adhesive performance, it is preferable that thermoplastic elastomer D has a structure different from that of thermoplastic elastomer A. Thermoplastic elastomer D may be different from thermoplastic elastomer A, and the structure of thermoplastic elastomer D is preferably the structure exemplified as the preferred structure of thermoplastic elastomer A described above. The thermoplastic elastomer D is not particularly limited, but examples thereof include the thermoplastic elastomers exemplified as the thermoplastic elastomer A. In the material for a pressure-sensitive adhesive of this embodiment, from the viewpoint of being more likely to exhibit stronger adhesive strength, it preferably contains a block copolymer (F) that, like the thermoplastic elastomer A, has a polymer block (D) mainly composed of vinyl aromatic monomer units and a polymer block (E) mainly composed of conjugated diene monomer units, and in which the number of polymer blocks (D) mainly composed of vinyl aromatic monomer units is one.

[0077] The vinyl aromatic hydrocarbon compound used to form the vinyl aromatic monomer unit is not particularly limited, but examples thereof include the vinyl aromatic hydrocarbon compounds exemplified in the thermoplastic elastomer A, and preferred vinyl aromatic hydrocarbon compounds include the preferred vinyl aromatic hydrocarbon compounds exemplified in the thermoplastic elastomer A. The conjugated diene compound is not particularly limited, but examples thereof include the conjugated diene compounds exemplified in the thermoplastic elastomer A, and preferred conjugated diene compounds include the preferred conjugated diene compounds exemplified in the thermoplastic elastomer A. The "polymer block (D) mainly composed of vinyl aromatic monomer units" may be synonymous with the "polymer block (A) mainly composed of vinyl aromatic monomer units" constituting the thermoplastic elastomer described above.

[0078] The content of the vinyl aromatic monomer unit in the thermoplastic elastomer D constituting the composition F is preferably within the range exemplified as the preferred content of the vinyl aromatic monomer unit in the thermoplastic elastomer A.

[0079] From the viewpoint of easily exhibiting even stronger adhesive strength in the pressure-sensitive adhesive material of this embodiment, it is preferable that the thermoplastic elastomer D contains a block copolymer (F) having a polymer block (D) mainly composed of vinyl aromatic monomer units and a polymer block (E) mainly composed of conjugated diene monomer units, and having one polymer block (D), as described above. From the same viewpoint, the content of the block copolymer (F) in the thermoplastic elastomer D is preferably within the range exemplified as the preferred content of the block copolymer (C) in the thermoplastic elastomer A.

[0080] From the same viewpoint, the weight average molecular weight of the block copolymer (F) having one polymer block (D) is preferably within the range exemplified as the preferred range of the weight average molecular weight of the block copolymer (C) having one polymer block (A) contained in the thermoplastic elastomer A described above.

[0081] The structure of the block copolymer (F) having one polymer block (D) is not particularly limited, and examples thereof include (AB), (AB)X, (BA)X, (BAB), and (BAB)X (where A represents polymer block (D), B represents polymer block (E), and X represents a residue of a coupling agent or a residue of a polymerization initiator). Among these, diblock copolymers represented by formula (AB) or formula (AB)X are preferred. When the block copolymer (F) has such a structure, a material for a pressure-sensitive adhesive tends to be obtained that is more likely to exhibit excellent adhesive strength, low melt viscosity, and high softening point.

[0082] Furthermore, the "thermoplastic elastomer D," which is one type of thermoplastic elastomer constituting composition F, preferably further contains a block copolymer (H-1) corresponding to the block copolymer (D-1) in the thermoplastic elastomer A constituting composition C, preferably further contains a block copolymer (H-2) corresponding to the block copolymer (D-2) in the thermoplastic elastomer A, and preferably further contains a block copolymer (H-3) corresponding to the block copolymer (D-3) in the thermoplastic elastomer A.

[0083] In the GPC elution curve, the preferred area ratio of the block copolymer (H-1), the preferred area ratio of the block copolymer (H-2), and the preferred area ratio of the block copolymer (H-3) relative to the total area of ​​the thermoplastic elastomer D can be exemplified from the same viewpoint as the preferred area ratio of the block copolymer (D-1), the preferred area ratio of the block copolymer (D-2), and the preferred area ratio of the block copolymer (D-3) relative to the total area of ​​the thermoplastic elastomer A.

[0084] Furthermore, in the GPC elution curve, the preferred ratio of the area of ​​block copolymer (H-2) to the area of ​​block copolymer (H-1) and the preferred ratio of the area of ​​block copolymer (H-3) to the area of ​​block copolymer (H-1) can be exemplified from the same viewpoints as the preferred ranges given as examples of the preferred ratio of the area of ​​block copolymer (D-2) to the area of ​​block copolymer (D-1) and the preferred ratio of the area of ​​block copolymer (D-3) to the area of ​​block copolymer (D-1) in elastomer A, respectively.

[0085] In the GPC elution curve, (i) the weight-average molecular weight ratio of block copolymer (H-1), block copolymer (H-2), and block copolymer (H-3) to block copolymer (F), and (ii) the area ratio in the GPC elution curve of block copolymer (H-1), block copolymer (H-2), and block copolymer (H-3) can be controlled within the above range by adjusting the coupling reaction conditions described below, specifically, the type of coupling agent, its addition amount, temperature, and time. For example, by selecting a compound containing four functional groups as a coupling agent, the weight-average molecular weight ratio and the area ratio in the GPC elution curve can be controlled.

[0086] The structures of block copolymers (H-1), (H-2), and (H-3) in thermoplastic elastomer D are not particularly limited and may consist of a single structure or a mixture having multiple types of structures. Specific structures include those exemplified as the structures of block copolymers (D-1), (D-2), and (D-3) in thermoplastic elastomer A, in which A represents polymer block (D) instead of polymer block (A), and B represents polymer block (E) instead of polymer block (B). Preferred structures also include those exemplified as preferred structures of block copolymers (D-1), (D-2), and (D-3).

[0087] A preferred hydrogenation rate H relative to the total amount of unsaturated double bonds derived from conjugated diene compounds in the polymer block (E) mainly composed of conjugated diene monomer units of the thermoplastic elastomer D is, from the same viewpoint as in the above-mentioned thermoplastic elastomer A, the range exemplified as a preferred range of the hydrogenation rate H relative to the total amount of unsaturated double bonds derived from conjugated diene compounds in the polymer block (B) mainly composed of conjugated diene monomer units.

[0088] Furthermore, from the same viewpoint, a preferable hydrogenation rate H relative to the total amount of unsaturated double bonds derived from the conjugated diene compound in the polymer block (E) mainly composed of conjugated diene monomer units may be in the range exemplified as a preferable range of the hydrogenation rate H relative to the total amount of unsaturated double bonds derived from the conjugated diene compound in the polymer block (E) mainly composed of conjugated diene monomer units.

[0089] (Composition C) The material for a pressure-sensitive adhesive of this embodiment contains composition C and composition F as described above. Composition C contains at least one thermoplastic elastomer A and has a particulate form. Composition C may contain at least one tackifier B, and in such a case, it is integrated with the thermoplastic elastomer A and has a particulate form.

[0090] (Composition F) Composition F contains at least one thermoplastic elastomer D and at least one tackifier E, which are integrated together and in the form of particles.

[0091] In the material for pressure-sensitive adhesives of this embodiment, The ratio of the total amount of thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is defined as x, In the composition C, the ratio of the total amount of the thermoplastic elastomers to the total amount of the total thermoplastic elastomers and the total amount of the tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, When the ratio of the total amount of the thermoplastic elastomers to the total amount of the thermoplastic elastomers and the total amount of the tackifiers in the composition F (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the material for a pressure-sensitive adhesive in which the ratio is x is greater than the adhesive strength of composition C in which the ratio is α, The adhesive strength is greater than that of composition F in which the ratio is β, The following formula (1) is satisfied. β <x<α (1) Here, "all thermoplastic elastomers" is not limited to the above-mentioned thermoplastic elastomers A and D, but refers to all thermoplastic elastomers contained in the pressure-sensitive adhesive material, composition C, and composition F, respectively. "Total tackifiers" is not limited to the above-mentioned tackifiers B and E, but refers to all tackifiers contained in the pressure-sensitive adhesive material, composition C, and composition F, respectively. The ratios x, α, and β are each a mass ratio. The adhesive strength is a value measured by the "Method for measuring adhesive strength (thermoplastic elastomer, each composition, and each dry blend composition)" described below. In the pressure-sensitive adhesive material of this embodiment, the adhesive strength of the pressure-sensitive adhesive material in which the ratio is x is greater than the adhesive strength of composition C in which the ratio is α, and greater than the adhesive strength of composition F in which the ratio is β, and by satisfying the following formula (1), even higher adhesive strength can be exhibited.

[0092] (Preferred Form of Material for Pressure-Sensitive Adhesives) Furthermore, from the viewpoint of being less prone to blocking, being easy to handle, and being able to exhibit high adhesive strength, it is preferable that composition C satisfies the following conditions (1) and / or (3), and composition F satisfies the following conditions (2) and / or (5). <Condition (1)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and 3.0 or less. <Condition (3)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition C is more than 60 mass% and less than 80 mass%, The proportion of the mass of all tackifiers relative to the total mass of the composition C is more than 20 mass % and less than 40 mass %. <Condition (2)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less. <Condition (4)> The ratio of the mass of all thermoplastic elastomers to the total mass of composition F is more than 20 mass% and less than 40 mass%, and the ratio of the mass of all tackifiers to the total mass of composition F is more than 60 mass% and less than 80 mass%.

[0093] The adhesive strength is highest when the thermoplastic elastomer and tackifier are mixed in an appropriate ratio, and the adhesive strength decreases when the ratio is deviated from that ratio. Therefore, both composition C, in which the thermoplastic elastomer ratio deviates from the appropriate ratio to the higher side, and composition F, in which the thermoplastic elastomer ratio deviates from the appropriate ratio to the lower side, have lower adhesive strength than when mixed in the appropriate ratio. By adjusting the ratio of composition C and composition F to be appropriate when mixed, the mixture is less likely to block and easier to handle before extrusion, and after extrusion, it is mixed together and exhibits high adhesive strength. By adjusting the ratio of the thermoplastic elastomer to be as close as possible within the range in which the adhesive strength of the composition C and the composition F is weak, it is possible to make the flow properties of the two compositions C and F similar. When the flow properties of the two compositions are similar, the time until they melt in the extruder and the viscosity when melted become similar, which tends to make them easier to mix uniformly, and as a result, it becomes easier to approach an appropriate ratio, which tends to improve the adhesive strength, and also tends to reduce the amount of unmelted material remaining, which tends to improve the appearance of the film.

[0094] More specifically, the composition ratio at which the adhesive strength in particulate form is sufficiently weak (to the extent that blocking does not become a problem) varies depending on the combination of thermoplastic elastomer and tackifier contained in Compositions C and F and the selection of the manufacturing equipment for the compositions; therefore, the composition ratio of thermoplastic elastomer and tackifier is adjusted so that the adhesive strength is weak depending on the thermoplastic elastomer, tackifier, manufacturing equipment, etc. Among these compositional ratios, the ratios of the thermoplastic elastomers in Compositions C and F are set to be close to each other as described above, and Compositions C and F are produced. The mass ratio of Compositions C and F is determined so that the ratio x of the total thermoplastic elastomer to the total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive material satisfies the above formula (1).

[0095] <Condition (1)> In composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier (mass of total thermoplastic elastomer / mass of total tackifier) ​​is preferably greater than 1.5 and equal to or less than 3.0. The lower limit of (mass of total thermoplastic elastomers / mass of total tackifiers) is preferably greater than 1.8, more preferably greater than 2.0, and even more preferably greater than 2.2. When the lower limit of the mass ratio of the total thermoplastic elastomer to the total tackifier is within the above range, the adhesive strength of composition C tends to be weaker, blocking is less likely to occur, and handling becomes easier. Furthermore, the upper limit of the mass ratio of total thermoplastic elastomer to total tackifier (mass of total thermoplastic elastomer / mass of total tackifier) ​​is more preferably 2.8 or less, even more preferably 2.6 or less, and even more preferably 2.4 or less. By keeping the upper limit of the mass ratio of all thermoplastic elastomers to all tackifiers within the above range, the fluidity of particulate composition C increases, becoming similar to that of composition F. In addition, when extruded by an extruder, it becomes easier to apply force evenly to the two types of particulate compositions, which tends to result in composition C being mixed uniformly with composition F. As a result, the adhesive strength of the pressure-sensitive adhesive formed upon extrusion tends to improve, the in-plane uniformity of the adhesive strength tends to improve, unmelted material tends to decrease, and the appearance of the film tends to improve.

[0096] <Condition (3)> The proportion of all tackifiers relative to the total mass of composition C is preferably more than 20 mass % and less than 40 mass %. The lower limit of the proportion is more preferably 23% by mass or more, even more preferably 26% by mass or more, and even more preferably 28% by mass or more. By setting the lower limit of the ratio within the above range, the fluidity of the particulate composition C increases, making it similar to the fluidity of composition F. In addition, when extruded by an extruder, it becomes easier to apply equal force to the two types of particulate compositions, which tends to mix uniformly with composition F. As a result, the adhesive strength of the pressure-sensitive adhesive formed upon extrusion tends to improve, the in-plane uniformity of the adhesive strength tends to improve, unmelted material tends to decrease, and the appearance of the film tends to improve. Furthermore, the upper limit of the ratio is more preferably 38% by mass or less, even more preferably 36% by mass or less, and even more preferably 34% by mass or less. When the upper limit of the ratio is within the above range, the adhesive strength of composition C tends to be weaker, blocking is less likely to occur, and handling becomes easier.

[0097] Furthermore, the proportion of the mass of all thermoplastic elastomers relative to the total mass of composition C is preferably more than 60 mass % and less than 80 mass %. The lower limit of the proportion is more preferably 62% by mass or more, even more preferably 64% by mass or more, and even more preferably 66% by mass or more. When the lower limit of the ratio is within the above range, the adhesive strength of composition C tends to be weak, blocking is less likely to occur, and handling becomes easier. Furthermore, the upper limit of the ratio is more preferably 78% by mass or less, even more preferably 76% by mass or less, and even more preferably 74% by mass or less. When the upper limit of the ratio is within the above range, the fluidity of particulate composition C increases, and the fluidity becomes similar to that of composition F. In addition, when extruded by an extruder, it becomes easier to apply force evenly to the two types of particulate compositions, and as a result, composition C tends to mix uniformly with composition F. Therefore, the adhesive strength of the pressure-sensitive adhesive formed during extrusion tends to improve, the in-plane uniformity of the adhesive strength tends to improve, unmelted material tends to decrease, and the appearance of the film tends to improve.

[0098] <Ratio α> In composition C, the ratio α of all thermoplastic elastomer to the total amount of all thermoplastic elastomer and all tackifier is preferably 0.6 or more and 0.8 or less, more preferably 0.62 or more and 0.78 or less, even more preferably 0.64 or more and 0.76 or less, and even more preferably 0.66 or more and 0.74 or less. When α is within the above range, composition C has low adhesive strength and is less likely to block, and also has higher fluidity than the thermoplastic elastomer alone, which tends to make it easier to mix with composition F.

[0099] <Ratio β> In composition F, the ratio β of the total amount of thermoplastic elastomer to the total amount of all thermoplastic elastomers and all tackifiers is preferably 0.2 or more and 0.4 or less, more preferably 0.22 or more and 0.38 or less, even more preferably 0.24 or more and 0.36 or less, and even more preferably 0.26 or more and 0.34 or less. When β is in the above range, the adhesive strength of composition F is low and it is less likely to block, and the fluidity is lower than that of the tackifier alone, so it tends to be easier to mix with composition C.

[0100] <Condition (2)> In composition F, the mass ratio of all tackifiers to all thermoplastic elastomers in composition F (mass of all tackifiers / mass of all thermoplastic elastomers) is preferably greater than 1.5 and equal to or less than 3.0. Composition F, having the above-described structure, has weak adhesive strength, making it less susceptible to blocking and easier to handle. The lower limit of the mass ratio of total tackifier to total thermoplastic elastomer in composition F (mass of total tackifier / mass of total thermoplastic elastomer) is more preferably greater than 1.8, even more preferably greater than 2.0, and even more preferably greater than 2.2. When the lower limit of the mass ratio of all tackifiers to all thermoplastic elastomers is within the above range, the adhesive strength of composition F tends to be weaker, blocking is less likely to occur, and handling becomes easier. Furthermore, the upper limit of the mass ratio of all tackifiers E to all thermoplastic elastomers in composition F (mass of all tackifiers / mass of all thermoplastic elastomers) is more preferably 3.0 or less, even more preferably 2.8 or less, even more preferably 2.6 or less, and still more preferably 2.4 or less. By keeping the upper limit of the mass ratio of all tackifiers to all thermoplastic elastomers within the above range, the fluidity is close to that of the aforementioned composition C. In addition, when extruded using an extruder, it becomes easier to apply equal force to the two types of particulate compositions. As a result, composition F tends to mix uniformly with composition C, which tends to improve the adhesive strength of the pressure-sensitive adhesive formed when extruded, tends to improve the in-plane uniformity of the adhesive strength, and tends to reduce unmelted material and improve the appearance of the film.

[0101] <Condition (4)> The proportion of the mass of all thermoplastic elastomers relative to the total mass of composition F is preferably 20% by mass or more and less than 40% by mass. The lower limit of the ratio is more preferably 23% by mass or more, even more preferably 26% by mass or more, and even more preferably 28% by mass or more. When the lower limit of the ratio is within the above range, the fluidity is close to that of the above-mentioned composition C, and at the same time, when extruded by an extruder, the force is easily applied evenly to the two types of particulate compositions. As a result, composition F tends to be mixed uniformly with composition C, and the adhesive strength of the pressure-sensitive adhesive formed during extrusion tends to be improved, the in-plane uniformity of the adhesive strength tends to be improved, and unmelted material tends to be reduced, tending to improve the appearance of the film. Furthermore, the upper limit of the ratio is more preferably 38% by mass or less, even more preferably 36% by mass or less, and even more preferably 34% by mass or less. When the upper limit of the ratio is within the above range, the adhesive strength of composition F tends to be weaker, blocking is less likely to occur, and handling becomes easier. Furthermore, the proportion of the mass of all tackifiers relative to the total mass of composition F is preferably more than 60 mass % and 80 mass % or less. The lower limit of the ratio is more preferably 62% by mass or more, even more preferably 64% by mass or more, and even more preferably 66% by mass or more. When the lower limit of the ratio is within the above range, the adhesive strength of composition F tends to be weaker, blocking is less likely to occur, and handling becomes easier. The upper limit of the proportion is more preferably 78% by mass or less, even more preferably 76% by mass or less, and even more preferably 74% by mass or less. By setting the upper limit of the ratio within the above range, the fluidity becomes similar to that of the aforementioned composition C, and in addition, when extruded by an extruder, it becomes easier to apply equal force to the two types of particulate compositions.As a result, composition F tends to mix uniformly with composition C, and the adhesive strength of the pressure-sensitive adhesive formed when extruded tends to improve, the in-plane uniformity of the adhesive strength tends to improve, unmelted material tends to decrease, and the appearance of the film tends to improve.

[0102] In composition F, the thermoplastic elastomer may be used alone or in combination of two or more types. Similarly, the tackifier may be used alone or in combination of two or more types. Furthermore, other components than those described above may also be appropriately contained. The other components may be the other components exemplified in the section on the pressure-sensitive adhesive composition of this embodiment described above.

[0103] In the pressure-sensitive adhesive material of this embodiment, the adhesive strength of Compositions C and F is preferably low, from the viewpoint of being less prone to blocking and being easy to handle. When the adhesive strength is measured according to the "Method for measuring adhesive strength (thermoplastic elastomer, each composition, and each dry blend composition)" described below, it is preferably 15.0 N / 10 mm or less, more preferably 14.0 N / 10 mm or less, even more preferably 13.0 N / 10 mm or less, even more preferably 12.0 N / 10 mm or less, particularly preferably 10.0 N / 10 mm or less, even more preferably 5.0 N / 10 mm or less, and even more preferably 1.0 N / 10 mm or less. Furthermore, from the same viewpoint, when the adhesive strength is measured according to the "Method for Measuring Tack Strength" (for the thermoplastic elastomer, each composition, and each dry blend composition) described below, the tack strength is preferably 10.0 N / 5 mmΦ or less, more preferably 8.0 N / 5 mmΦ or less, even more preferably 6.0 N / 5 mmΦ or less, even more preferably 5.0 N / 5 mmΦ or less, even more preferably 3.0 N / 5 mmΦ or less, and particularly preferably 1.0 N / 5 mmΦ or less.

[0104] In the material for a pressure-sensitive adhesive of this embodiment, composition C and composition F may be mixed or may be separate. For example, when composition C and composition F are packaged together, they are classified as a mixed form, and when they are packaged separately as a set, they are classified as a separated form. Compositions C and F each have low adhesive strength when used alone, and are therefore less likely to block and easier to handle during the process from the pressure-sensitive adhesive material to the pressure-sensitive adhesive, making them suitable for distribution.

[0105] (Ratio of the amounts of composition C and composition F) In the material for a pressure-sensitive adhesive of this embodiment, it is preferable to dry-blend Composition C and Composition F to form a dry blend (dry-blend composition) before the extrusion step described below, which results in a more uniform pressure-sensitive adhesive. The blending mass ratio of composition C to composition F (blended mass of composition C / blended mass of composition F) in the material for pressure-sensitive adhesives of this embodiment (e.g., a dry blend) is not particularly limited, but is preferably 0.45 or more and 2.00 or less, more preferably 0.50 or more and 1.90 or less, even more preferably 0.55 or more and 1.80 or less, and even more preferably 0.60 or more and 1.70 or less. By keeping the mass ratio of (composition C / composition F) within the above range, compositions C and F tend to be more homogenized during extrusion molding, which tends to result in a material for pressure-sensitive adhesives that is more likely to exhibit even better adhesive strength.

[0106] Compositions C and F in the material for pressure-sensitive adhesives of this embodiment (e.g., a dry blend) are in a particulate form, from the viewpoints of suppressing classification during extrusion molding and facilitating the formation of highly uniform pressure-sensitive adhesives. Furthermore, in the material for a pressure-sensitive adhesive of this embodiment (e.g., a dry blend), it is preferable to satisfy the following <Condition (5)>, from the viewpoints of suppressing classification during extrusion molding and facilitating the formation of a highly uniform pressure-sensitive adhesive when made into a pressure-sensitive adhesive. Furthermore, from the viewpoint of forming a highly uniform pressure-sensitive adhesive, the material for a pressure-sensitive adhesive of this embodiment preferably satisfies the following <Condition (6)>.

[0107] <Condition (5)> The ratio (Wc / Wf) of the average particle mass Wc of composition C to the average particle mass Wf of composition F is preferably 0.4 or more and 2.5 or less, more preferably 0.4 or more and 2.3 or less, even more preferably 0.5 or more and 2.0 or less, and even more preferably 0.6 or more and 1.5 or less.

[0108] <Condition (6)> The ratio of the average particle length Lc of composition C to the average particle length Lf of composition F is preferably 0.6 or more and 1.4 or less, more preferably 0.7 or more and 1.3 or less, even more preferably 0.8 or more and 1.2 or less, and even more preferably 0.9 or more and 1.1 or less. The ratio of the average particle minor diameter lc of composition C to the average particle minor diameter lf of composition F is preferably 0.6 or more and 1.4 or less, more preferably 0.7 or more and 1.3 or less, even more preferably 0.8 or more and 1.2 or less, and even more preferably 0.9 or more and 1.1 or less. The average particle mass, average particle length, and average particle length of the composition can be measured by the methods described in the Examples below.

[0109] The mass proportion of the total thermoplastic elastomer in the material for pressure-sensitive adhesives of this embodiment (e.g., a dry blend) is preferably 30 mass% or more, more preferably 35 mass% or more, even more preferably 40 mass% or more, and even more preferably 45 mass% or more. By having the mass ratio of the total thermoplastic elastomer in the pressure-sensitive adhesive material of this embodiment within the above range, there is a tendency for a pressure-sensitive adhesive material to be obtained that is more likely to exhibit even better adhesive strength, tack strength, and holding power. Furthermore, from the viewpoint that there is a tendency to obtain a material for a pressure-sensitive adhesive that is more likely to exhibit even higher adhesive strength, the mass proportion of all thermoplastic elastomers (including the thermoplastic elastomers in Compositions C and F) in the material for a pressure-sensitive adhesive (e.g., a dry blend) is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, and even more preferably 65 mass% or less.

[0110] In the material for pressure-sensitive adhesives of this embodiment, from the viewpoint that a material for pressure-sensitive adhesives that is more likely to exhibit even better adhesive strength, tackiness, and holding power is obtained, the mass ratio of the total tackifier in the material for pressure-sensitive adhesives (e.g., a dry blend) is preferably 70 mass% or less, more preferably 65 mass% or less, even more preferably 60 mass% or less, and even more preferably 55 mass% or less. Furthermore, from the viewpoint that a material for a pressure-sensitive adhesive (e.g., a dry blend) that is more likely to exhibit even better adhesive strength is obtained, the mass ratio of the total tackifier in the material for a pressure-sensitive adhesive (e.g., a dry blend) is preferably 20 mass% or more, more preferably 25 mass% or more, even more preferably 30 mass% or more, and even more preferably 35 mass% or more.

[0111] (Other ingredients) The material for a pressure-sensitive adhesive of this embodiment may contain any component within a range that does not impair the effects of the present invention. The optional components are not particularly limited, but include, for example, antioxidants, optional polymers, waxes, stabilizers such as light stabilizers, and other additives.

[0112] <Antioxidants> 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-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,4-bis[(octylthio)methyl]-0-cresol, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-t-butyl ... Examples of antioxidants include hindered phenol-based antioxidants such as myl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate and 2-[1-(2-hydroxy-3,5-di-tErt-pentylphenyl)]acrylate; sulfur-based antioxidants such as dilauryl thiodipropionate and lauryl stearyl thiodipropionate pentaerythritol-tetrakis(β-lauryl thiopropionate); and phosphorus-based antioxidants such as tris(nonylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite. Specific examples of commercially available antioxidants include Sumilizer GM (trade name), Sumilizer TPD (trade name), and Sumilizer TPS (trade name) manufactured by Sumitomo Chemical Co., Ltd., Irganox 1010 (trade name), Irganox HP2225FF (trade name), Irgafos 168 (trade name), and Irganox 1520 (trade name) manufactured by Ciba Specialty Chemicals, Inc., and JF77 (trade name) manufactured by Johoku Chemical Co., Ltd. These stabilizers can be used alone or in combination.

[0113] <Any polymer> The optional polymer is not limited to the following, but examples thereof include polyolefin copolymers, vinyl aromatic copolymers, and other rubbers. Examples of polyolefin copolymers include, but are not limited to, atactic polypropylene, ethylene-ethyl acrylate copolymers, and α-olefin polymers. Examples of vinyl aromatic copolymers include, but are not limited to, styrene-ethylene block copolymers, styrene-butadiene block copolymers, styrene-propylene block copolymers, styrene-isoprene block copolymers, styrene-butadiene-isoprene block copolymers, styrene-butadiene / isoprene block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene-isoprene block copolymers, hydrogenated styrene-butadiene / isoprene block copolymers, etc. The vinyl aromatic copolymer may be a vinyl aromatic thermoplastic resin or a vinyl aromatic elastomer. Examples of other rubbers include, but are not limited to, natural rubber; and synthetic rubbers such as isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, propylene-butylene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, and polypentenamer rubber. Preferred optional polymers depending on the application and performance will be described in more detail below.

[0114] <Hydrogenated vinyl aromatic copolymer> When reduction of adhesive residue when peeling off the pressure-sensitive adhesive material of this embodiment, suppression of change in adhesive strength over time or creep resistance (smaller values ​​are better), thermal stability, light resistance, etc. are required, hydrogenated vinyl aromatic copolymers can be suitably used. Examples of hydrogenated vinyl aromatic copolymers include, but are not limited to, hydrogenated styrene-butadiene block copolymers having a structure such as S-EB-S (S: polystyrene block, EB: ethylene / butylene copolymer block); hydrogenated styrene-isoprene block copolymers having a structure such as S-EP-S (S: polystyrene block, EP: ethylene / propylene copolymer block); and hydrogenated styrene-butadiene-isoprene block copolymers having a structure such as SE-EP-S (S: polystyrene block, E: ethylene block, EP: ethylene / propylene copolymer block). The styrene content of the hydrogenated vinyl aromatic copolymer is preferably 10% by mass to 45% by mass relative to 100% by mass of the hydrogenated vinyl aromatic copolymer. The hydrogenation rate of unsaturated groups in the conjugated diene monomer units in the hydrogenated vinyl aromatic copolymer is preferably 30% by mole or more, more preferably 50% by mole or more, even more preferably 70% by mole or more, and still more preferably 85% by mole or more.

[0115] <Isoprene-based block copolymer> When high adhesiveness, suppression of gelation, and the like are required as the pressure-sensitive adhesive material of this embodiment, an isoprene-based block copolymer having an isoprene monomer unit can be suitably used. The isoprene-based block copolymer is not limited to the following, but for example, (SI) n , (SI) n -S, (SI) n Styrene-isoprene block copolymers having structures such as Y (S: polystyrene block, I: polyisoprene block); (SIB) n , (SIB) n -S, (SIB) n Y (S: polystyrene block, I: polyisoprene block, B: polybutadiene block, Y: residue of a polyfunctional coupling agent or residue of a polymerization initiator, n is an integer of 1 or more, preferably an integer of 1 to 5), or (SI / B) n , (SI / B) n-S, (SI / B) n Examples include styrene-butadiene-isoprene block copolymers having a structure such as Y (S: polystyrene block, I / B: isoprene / butadiene copolymer block, Y: residue of a coupling agent or residue of a polymerization initiator, n is an integer of 1 or more, preferably an integer of 1 to 5). These preferably have a radial structure.

[0116] <Ionomer> When high low-temperature coating properties, creep properties (smaller values ​​are better), high strength or high elongation are required for the pressure-sensitive adhesive material of this embodiment, the polymer may be used in the form of an ionomer. Preferred ionomers include, but are not limited to, homopolymers or copolymers containing carboxylates, sulfonates, or phosphonates neutralized or partially neutralized with metal ions. The content of the ionomer is preferably 5% by mass or less based on the total amount of the material for a pressure-sensitive adhesive.

[0117] <Polyolefin copolymer> In the pressure-sensitive adhesive material of this embodiment, when it is necessary to improve high-temperature storage stability and high elongation and reduce the amount of tackifier in the pressure-sensitive adhesive material, a polyolefin copolymer can be used. The polyolefin copolymer is preferably, but not limited to, a copolymer of an α-olefin and an olefin, or a propylene homopolymer. The melting point of these polymers (conditions: DSC measurement, 5°C / min) is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 60°C to 90°C. These polymers may be thermoplastic resins or elastomers. The molecular weight distribution of these polymers is preferably 1 to 4, more preferably 1 to 3. From the viewpoint of processability, it is more preferable to use two or more types of copolymers using α-olefins or propylene homopolymers in combination. Specifically, it is preferable to use a polymer having a weight-average molecular weight of 30,000 to 60,000 in combination with a polymer having a weight-average molecular weight of 60,000 to 90,000, and it is more preferable to use a polymer having a weight-average molecular weight of 35,000 to 55,000 in combination with a polymer having a weight-average molecular weight of 60,000 to 80,000.

[0118] <Conjugated diene rubber> In the pressure-sensitive adhesive material of this embodiment, a conjugated diene rubber can be suitably used as the optional polymer. Examples of conjugated diene rubbers include, but are not limited to, isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, and propylene-butylene rubber. Among these, polyisoprene rubber is more preferred from the viewpoint of high effectiveness. The content of the conjugated diene rubber is preferably 0% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less, relative to the total amount of the material for pressure-sensitive adhesives.

[0119] <Olefin elastomer> When elongation or the like is required as a material for a pressure-sensitive adhesive, it is preferable to use an olefin-based elastomer as the optional polymer. The olefin-based elastomer is not limited to the following, but is preferably one having a Tg of −10° C. or less. Furthermore, from the viewpoint of creep performance (the smaller the value, the better), an olefin-based elastomer having blocks is more preferred.

[0120] <Wax> The pressure-sensitive adhesive material may contain wax as needed. Examples of waxes include, but are not limited to, paraffin wax, microcrystalline wax, and low molecular weight polyethylene wax. When a low melt viscosity is required for a material for a pressure-sensitive adhesive, it is preferable to use at least one wax selected from paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. The wax content is preferably 2 to 10% by mass, and more preferably 5 to 10% by mass. The melting point of the wax is preferably 50°C to 110°C, more preferably 65°C to 110°C, even more preferably 70°C to 110°C, and even more preferably 75°C to 110°C. The softening point of the tackifier used in combination is preferably 70°C or higher, more preferably 80°C or higher. The G' (measurement conditions: 25°C, 10 rAD / s) of the resulting pressure-sensitive adhesive material is preferably 1 MPa or lower. The crystallization temperature of the pressure-sensitive adhesive material is preferably 7°C or lower.

[0121] <Light stabilizer> The pressure-sensitive adhesive material may contain a light stabilizer, if necessary. Examples of light stabilizers include, but are not limited to, benzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-t-butylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole; benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; and hindered amine-based light stabilizers.

[0122] <Fine particle filler> A particulate filler may be further added as another additive to the pressure-sensitive adhesive material of this embodiment. The particulate filler is not particularly limited as long as it is a commonly used one. The particulate filler is not particularly limited, but examples thereof include mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, etc. The shape of these is preferably spherical, and the dimensions (diameter in the case of a spherical shape) are not particularly limited.

[0123] As components other than the above-mentioned (other components), a softener or the like can be used. The softener is a substance that has the function of lowering the hardness and viscosity of the pressure-sensitive adhesive material. The softener may include, but is not limited to, oils; plasticizers; synthetic liquid oligomers; and mixtures thereof. From the viewpoint of reducing the viscosity of the pressure-sensitive adhesive material, improving adhesion, and reducing hardness, it is preferable to use oils. The oils are not limited to the following, but examples thereof include known paraffin-based process oil, naphthene-based process oil, aromatic process oil, and mixtures thereof. The softener may be used alone or in combination of two or more kinds. When used as food packaging, from the viewpoint of preventing the transfer of the softener to food due to bleed-out of the softener, the content of the softener is preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably substantially free of the softener, relative to the entire pressure-sensitive adhesive material. This "substantially free of" means that the softener is not excluded even in an amount that is unavoidably mixed into the production plant, materials, etc.

[0124] [Pressure-sensitive adhesive] The pressure-sensitive adhesive of this embodiment includes the material for a pressure-sensitive adhesive of this embodiment. In this specification, the term "pressure-sensitive adhesive" refers to an adhesive that bonds by simply applying pressure for a short period of time at room temperature. The form of the "pressure-sensitive adhesive" is not particularly limited, and may be, for example, a layer form (hereinafter, sometimes referred to as a "pressure-sensitive adhesive layer"). The adhesive strength can be measured by the "Method for measuring adhesive strength (thermoplastic elastomer, each composition, and each dry blend composition)" or "(Adhesive strength of three-layer film)" described in the Examples below. The pressure-sensitive adhesive of this embodiment preferably exhibits an adhesive strength of 1.5 N / 10 mm or more when measured by an adhesive strength measurement method (three-layer film). When the adhesive strength is within the above range, the adhesive can be suitably used in applications requiring strong adhesive strength, such as resealable packaging. From a similar viewpoint, the adhesive strength of the pressure-sensitive adhesive of this embodiment is more preferably 2.0 N / 10 mm or more, even more preferably 2.2 N / 10 mm or more, even more preferably 2.4 N / 10 mm or more, even more preferably 2.6 N / 10 mm or more, even more preferably 2.8 N / 10 mm or more, even more preferably 3.0 N / 10 mm or more, even more preferably 3.2 N / 10 mm or more, even more preferably 3.4 N / 10 mm or more, even more preferably 3.6 N / 10 mm or more, even more preferably 3.8 N / 10 mm or more, even more preferably 4.0 N / 10 mm or more, and even more preferably 4.2 N / 10 mm or more.

[0125] [Multilayer film] The multilayer film of this embodiment includes the pressure-sensitive adhesive of this embodiment. The multilayer film of this embodiment can be obtained, for example, by co-extruding the pressure-sensitive adhesive material of this embodiment and another material, as a multilayer film having a configuration including a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of this embodiment. The multilayer film of the present embodiment includes two or more layers, preferably three or more layers, and more preferably includes the pressure-sensitive adhesive layer of the present embodiment in a layer other than the outermost layer. This tends to prevent blocking during film winding and makes handling even easier.

[0126] The thickness of the pressure-sensitive adhesive layer in the multilayer film of this embodiment is preferably 5 μm or more, more preferably 8 μm or more, even more preferably 10 μm or more, even more preferably 12 μm or more, and even more preferably 14 μm or more, from the viewpoint of exhibiting high adhesive strength, and is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and even more preferably 25 μm or less, from the viewpoint of economy.

[0127] [Packaging] The packaging body of this embodiment includes the multilayer film of this embodiment. That is, when the multilayer film of the present embodiment is used as a lid material for a packaging material to obtain a package, it is possible to provide a package in which, when the lid material is peeled from the package, it is peeled at the interface between the pressure-sensitive adhesive layer and the other material layer or inside the pressure-sensitive adhesive layer. In such a package, the pressure-sensitive adhesive layer is exposed at the outermost surface after the lid material is peeled from the package, so that it exhibits strong adhesive strength and can be made into a resealable package.

[0128] The packaging body of this embodiment includes the multilayer film of this embodiment, and can be produced by heat-sealing the above-described multilayer film of this embodiment to a packaging body.

[0129] [Method for producing a material for pressure-sensitive adhesive] The pressure-sensitive adhesive material of this embodiment can be obtained by mixing the above-mentioned Composition C and Composition F. Compositions C and F can be obtained by mixing the above-mentioned thermoplastic elastomer and tackifier in any desired blending ratio.

[0130] The thermoplastic elastomers constituting Compositions C and F can be produced by the following method. (Method of producing thermoplastic elastomers A and D constituting compositions C and F) <Polymerization process, coupling process> The method for producing the thermoplastic elastomers A and D is not particularly limited, and known methods can be used. The following describes an example of a method for producing a thermoplastic elastomer containing a polymer block mainly composed of vinyl aromatic monomer units and a polymer block mainly composed of conjugated diene monomer units. Examples of methods for producing thermoplastic elastomers include a polymerization step of copolymerizing a vinyl aromatic hydrocarbon compound such as styrene and a conjugated diene compound such as butadiene in an inert hydrocarbon solvent using an organolithium compound as a polymerization initiator to obtain a block copolymer, and a coupling step of reacting the obtained block copolymer with a coupling agent. In this case, for example, the coupled block copolymer becomes any one of the above-mentioned block copolymers (D-1), (D-2), and (D-3), and the remaining block copolymer that is not coupled becomes block copolymer (C) having one polymer block (A) mainly composed of vinyl aromatic monomer units. In this coupling reaction, the contents of the block copolymer (C) and the block copolymers (D-1), (D-2), and (D-3) can be adjusted to fall within the above-mentioned ranges by controlling the amount of coupling agent added. Alternatively, such thermoplastic elastomers A and D can be obtained by separately polymerizing the block copolymer (C) and the block copolymers (D-1), (D-2), and (D-3) and then mixing them.

[0131] The weight-average molecular weight of the block copolymer can be adjusted by controlling the amount of initiator such as an organolithium compound. After the polymerization reaction is completed, a coupling reaction is carried out, and water, an alcohol, an acid, or the like is added to deactivate the active species. The polymerization solvent is separated by, for example, steam stripping, and then the mixture is dried to obtain block copolymers (C), (D-1), (D-2), and (D-3).

[0132] The polymerization method for the block copolymer is not limited to the following, but examples thereof include coordination polymerization, anionic polymerization, and cationic polymerization. Among these, anionic polymerization is preferred from the viewpoint of ease of control of the structure. The method for producing the block copolymer component by anionic polymerization can be a known method, and is not particularly limited. Examples of the method include those described in JP-B-36-19286, JP-B-43-17979, JP-B-46-32415, JP-B-49-36975, JP-B-48-2423, JP-B-48-4106, JP-B-56-28925, JP-A-59-166518, and JP-A-60-186577.

[0133] Examples of inert hydrocarbon solvents used in the polymerization step of the block copolymer include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.

[0134] The organolithium compound used as a polymerization initiator in the polymerization step of the block copolymer is not particularly limited, and known compounds can be used, such as ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, propenyllithium, hexyllithium, etc. In particular, n-butyllithium and sec-butyllithium are preferred. The organolithium compounds may be used alone or in combination of two or more.

[0135] By the above-mentioned method, the block copolymer contained in the thermoplastic elastomer can be obtained as a block copolymer represented by any one of the following formulas. (AB) N , (AB) N X, (AB) N A, [(AB) N ] m , (AB)N AX, (BA) N X, (BA) N B, (BA) N BX〔(AB) N 〕 m X, 〔(BA) N 〕 m X, 〔(AB) N A) m X, 〔(BA) N B] m X (In the above formula, A is the polymer block (A), and B is the polymer block (B). X represents a residue of a coupling agent or a residue of a polymerization initiator. N is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 to 8, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.) Among these, the above-mentioned coupling reaction can be used to produce block copolymer (C): Formula (AB) and multi-branched block copolymers (D-1), (D-2), and (D-3): Formula (AB) m It is preferable to prepare X and

[0136] As the coupling agent for obtaining the multi-branched block copolymer, known coupling agents can be used. Examples of bifunctional coupling agents include, but are not limited to, bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional alkoxysilanes such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane; bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, and dibromomethane; bifunctional tin halides such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, and dibutyldichlorotin; dibromobenzene, benzoic acid, CO, and 2-chloropropene. Examples of trifunctional coupling agents include, but are not limited to, trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; and trifunctional alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Examples of tetrafunctional coupling agents include, but are not limited to, tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane; tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; and tetrafunctional tin compounds such as tetrachlorotin, tetrabromotin, and tetrabutyltin. Examples of the pentafunctional or higher coupling agent include, but are not limited to, 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, and decabromodiphenyl ether. In addition, epoxidized soybean oil, di- to hexa-functional epoxy group-containing compounds, carboxylic acid esters, and polyvinyl compounds such as divinylbenzene can also be used. The coupling agent may be used alone or in combination of two or more. Among these, tetramethoxysilane and tetraethoxysilane are particularly preferred.

[0137] The area ratios of the block copolymers (D-1), (D-2), and (D-3) in the GPC elution curves can be controlled by adjusting the amount of coupling agent added, the temperature, and the time in the coupling reaction, as described above. Specifically, when the coupling agent is an alkoxysilane compound, the time from when the reaction temperature reaches the maximum temperature until the coupling agent is added is set to 1 to 30 minutes, the reaction time of the coupling agent is set to 1 to 60 minutes, the reaction temperature is set to 55 to 100°C, and the amount of coupling agent added is adjusted so that the molar ratio to the total number of moles of polymerization initiator is 0.025 to 0.30. In addition, when the coupling agent is other than an alkoxysilane compound, the time from when the reaction temperature reaches the maximum temperature until the coupling agent is added is set to 1 to 30 minutes, the reaction time of the coupling agent is set to 1 to 35 minutes, the reaction temperature is set to 50 to 95°C, and the amount of coupling agent added is adjusted so that the molar ratio to the total number of moles of polymerization initiator is 0.025 to 0.20. A deactivator may also be added during polymerization of the block copolymer (C). In this case, a component (C)' with a relatively low molecular weight is produced. Specifically, after polymerization of the vinyl aromatic monomer units, a deactivator may be added at any point during polymerization of the conjugated diene monomer units in an amount that deactivates 50% by mass or less without completely deactivating the units, to produce a diblock copolymer (C)' represented by general formula (A-B') (where B' represents the polymer block (B) obtained by deactivation during polymerization). The content of the diblock copolymer represented by general formula (A-B') is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the block copolymer composition. The inclusion of the diblock copolymer (C)' represented by general formula (A-B') tends to further improve adhesive strength and holding power.

[0138] <Hydrogenation reaction> When part or all of the unsaturated double bonds of the block copolymer derived from the conjugated diene compound are hydrogenated, the hydrogenation method is not particularly limited, and can be carried out using a known technique using a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and known catalysts can be used. Examples of the hydrogenation catalyst include supported heterogeneous hydrogenation catalysts in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, or diatomaceous earth; so-called Ziegler-type hydrogenation catalysts that use a transition metal salt such as an organic acid salt or an acetylacetonate salt of Ni, Co, FE, Cr, or the like, and an organoaluminum or other reducing agent; and homogeneous hydrogenation catalysts such as so-called organometallic complexes of organometallic compounds such as Ti, Ru, Rh, or Zr. Specifically, the hydrogenation catalysts described in Japanese Patent Publication Nos. 42-8704, 43-6636, 63-4841, 1988-37970, 1989-53851, and 2-9041 can be used. Among these, preferred hydrogenation catalysts include titanocene compounds, reducing organometallic compounds, and mixtures thereof. The titanocene compound is not particularly limited, but examples thereof include the compounds described in JP-A-8-109219. Specific examples include compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyltitanium dichloride and monopentamethylcyclopentadienyltitanium trichloride. The reducing organometallic compound is not particularly limited, but examples thereof include organic alkali metal compounds such as organolithium compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds. The hydrogenation reaction temperature is preferably 0 to 200°C, more preferably 30 to 150°C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa. Furthermore, the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction may be a batch process, a continuous process, or a combination thereof. The target block copolymer can be obtained by removing catalyst residues, if necessary, from the block copolymer solution obtained through the hydrogenation reaction and separating the solution. The method for separating the solvent is not particularly limited, and examples include a method in which a polar solvent that is a poor solvent for the hydrogenated block copolymer, such as acetone or alcohol, is added to the reaction solution after hydrogenation to precipitate and recover the polymer, a method in which the reaction solution after hydrogenation is poured into hot water with stirring and the solvent is removed by steam stripping to recover the polymer, and a method in which the reaction solution after hydrogenation is heated to distill off the solvent.

[0139] Furthermore, the amount (mass%) of the polymer block (A) mainly composed of vinyl aromatic monomer units relative to the total amount (100 mass%) of vinyl aromatic monomer units used to polymerize the block copolymer, i.e., the block ratio, is preferably 90 mass% or more, more preferably 95 mass% or more, and even more preferably 97 mass% or more. When the block ratio is within the above range, a block copolymer having excellent finishability tends to be obtained, and the pressure-sensitive adhesive material of the present embodiment containing this block copolymer tends to have excellent adhesive strength and holding power. The amount of polymer block mainly composed of vinyl aromatic monomer polymers can be determined by dissolving the block copolymer in chloroform, adding an osmonic acid / tertiary butyl hydroperoxide solution to cleave the double bond of the butadiene component, adding methanol, filtering, dissolving the residue in chloroform, and measuring the peak intensity (absorption wavelength: 262 nm) of the resulting solution with an ultraviolet spectrophotometer to calculate the block styrene content.

[0140] In the production methods of the thermoplastic elastomers A and D used in Compositions C and F, a step of decalcifying metals derived from the polymerization initiator, etc. may be employed as needed. In addition, in the production methods of the thermoplastic elastomers A and D, a step of adding an antioxidant, a neutralizing agent, a surfactant, etc. may be further employed as needed. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds, phosphorus compounds, sulfur compounds, and the like, which will be described later. Examples of the neutralizing agent include, but are not limited to, various metal stearates, hydrotalcite, benzoic acid, and the like. Examples of surfactants include, but are not limited to, anionic surfactants, nonionic surfactants, cationic surfactants, etc. Examples of anionic surfactants include, but are not limited to, fatty acid salts, alkyl sulfate ester salts, alkylaryl sulfonates, etc. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, etc. Examples of cationic surfactants include, but are not limited to, alkylamine salts, quaternary ammonium salts, etc.

[0141] The thermoplastic elastomer that can be produced as described above may include a so-called modified block copolymer in which a polar group-containing functional group containing an atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin is bonded to a block copolymer, or a modified block copolymer in which a block copolymer component is modified with a modifier such as maleic anhydride. Such a modified block copolymer can be obtained, for example, by subjecting the block copolymer obtained by the above method to a known modification reaction. The method for imparting these functional groups is not particularly limited, but examples thereof include a method of adding functional groups to a polymer using a compound having a functional group in a polymerization initiator, a monomer, a coupling agent, or a terminator. As the polymerization initiator containing a functional group, a polymerization initiator containing an N group is preferred, and examples thereof include dioctylaminolithium, di-2-ethylhexylaminolithium, ethylbenzylaminolithium, (3-(dibutylamino)-propyl)lithium, and piperidinolithium. Furthermore, examples of monomers containing a functional group include compounds containing a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, or an alkoxysilane group in addition to the monomers used in the polymerization. Among these, monomers containing an N group are preferred, and examples thereof include N,N-dimethylvinylbenzylamine, N,N-diethylvinylbenzylamine, N,N-dipropylvinylbenzylamine, N,N-dibutylvinylbenzylamine, N,N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis(trimethylsilyl)aminoethylstyrene, 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene, Examples thereof include N,N-dimethyl-2-(4-vinylbenzyloxy)ethylamine, 4-(2-pyrrolidinoethyl)styrene, 4-(2-piperidinoethyl)styrene, 4-(2-hexamethyleneiminoethyl)styrene, 4-(2-morpholinoethyl)styrene, 4-(2-thiazinoethyl)styrene, 4-(2-N-methylpiperazinoethyl)styrene, 1-((4-vinylphenoxy)methyl)pyrrolidine, and 1-(4-vinylbenzyloxymethyl)pyrrolidine. Furthermore, coupling agents and terminators containing functional groups include the above-mentioned coupling agents, such as compounds containing hydroxyl groups, acid anhydride groups, epoxy groups, amino groups, amide groups, silanol groups, and alkoxysilane groups. Among these, coupling agents containing N groups or O groups are preferred, such as tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyl diaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldiethylethoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0142] After the thermoplastic elastomer is produced as described above, the block copolymer is isolated, that is, finished, by the method described below. When the polymerization process for the block copolymer is carried out in an inert hydrocarbon solvent, the block copolymer is isolated by removing the inert hydrocarbon solvent. Steam stripping is a specific example of a method for removing the solvent. A hydrous crumb is obtained by steam stripping, and the resulting hydrous crumb is then dried to obtain the block copolymer. In steam stripping, a surfactant is preferably used as a crumbing agent. Examples of such surfactants include, but are not limited to, the anionic surfactants, cationic surfactants, and nonionic surfactants described above. These surfactants can generally be added in an amount of 0.1 to 3,000 ppm to the water in the stripping zone. In addition to surfactants, water-soluble salts of metals such as Li, Na, Mg, Ca, Al, and Zn can also be used as crumb dispersing aids. The concentration of the crumb-like block copolymer dispersed in water obtained through the block copolymer polymerization step and the steam stripping is generally 0.1 to 20% by mass (ratio to the water in the stripping zone). This range allows crumbs with good particle size to be obtained without operational problems. It is preferable to adjust the water content of the block copolymer crumbs to 1 to 30% by mass by dehydration, and then dry them until the water content is 1% by mass or less. In the crumb dehydration step, dehydration can be performed using a compressed water squeezer such as a roll, a Banbury dehydrator, or a screw extruder squeezer dehydrator, or dehydration and drying can be performed simultaneously using a conveyor or a box-type hot air dryer.

[0143] (Production methods of compositions C and F) The method for producing compositions C and F is not particularly limited, and known methods can be used. For example, a method can be used in which a thermoplastic elastomer and a tackifier are mixed at a desired mixing ratio using a device equipped with kneading functions such as heating and stirring, such as a single-screw or twin-screw extruder, a mixer, or a kneader, and the mixture is melt-extruded into water or taken out onto a cooling belt to cool and solidify, and then cut into an appropriate size to form pellets, beads, or other particles. When the mixture is melt-extruded into water, for example, it can be cut into particles such as pellets using an underwater cutting granulator. The temperature during kneading varies depending on the composition, the equipment used, etc., but is usually 100 to 250°C, preferably 120 to 180°C, and the kneading time is usually 10 to 120 minutes, preferably 15 to 60 minutes.

[0144] In the method for producing compositions C and F, the composition may be cut in water, followed by a dehydration / drying step of dehydrating and drying, and after the dehydration / drying step, a step of attaching an antiblocking agent as a post-addition may be carried out. After dehydration, an anti-blocking agent may be applied and then the material may be dried. Alternatively, a step of adding an anti-blocking agent to the water to adhere the anti-blocking agent to the surface of the composition may be carried out. The dehydration and drying method is not particularly limited, but a centrifugal dehydrator or the like can be used.

[0145] [Method of forming pressure-sensitive adhesive] The method for producing a pressure-sensitive adhesive of this embodiment includes an extrusion step of extruding, in an extruder, a particulate composition C containing at least one thermoplastic elastomer A and at least one tackifier B, which are integrated together, and a particulate composition F containing at least one thermoplastic elastomer D and at least one tackifier E, which are integrated together, to obtain a pressure-sensitive adhesive. The pressure-sensitive adhesive is contained in a resealable packaging multilayer film. Composition C satisfies the following conditions (7) and / or (9), and composition F satisfies the following conditions (8) and / or (10). In this case, it is preferable that the following <Condition (7)> ​​and <Condition (8)> are satisfied together, and that the following <Condition (9)> and <Condition (10)> are satisfied together.

[0146] <Condition (7)> The ratio of the total thermoplastic elastomer to the total tackifier in composition C The mass ratio is greater than 1.5 and equal to or less than 3.0. <Condition (8)> The ratio of the total tackifier to the total thermoplastic elastomer in the composition F The mass ratio is greater than 1.5 and equal to or less than 3.0. <Condition (9)> The total mass of the thermoplastic elastomer relative to the total mass of the composition C The mass ratio is more than 60 mass% and less than 80 mass%, The ratio of the mass of all tackifiers to the mass of the entire composition C is More than 20% by mass and less than 40% by mass. <Condition (10)> The total mass of the thermoplastic elastomer relative to the total mass of the composition F The mass ratio is more than 20 mass% and less than 40 mass%, The ratio of the mass of all tackifiers to the mass of the entire composition F is More than 60% by mass and less than 80% by mass.

[0147] In the extrusion process, if the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is y, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in composition C is α, and the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in composition F (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is β, the adhesive strength of a pressure-sensitive adhesive material having a ratio of y is greater than the adhesive strength of composition C having a ratio of α, and is greater than the adhesive strength of composition F having a ratio of β. In addition, α, β, and y satisfy the following formula (2). β <y<α (2)

[0148] The method for producing a pressure-sensitive adhesive of this embodiment, by having the above-described configuration, can produce a pressure-sensitive adhesive that is resistant to blocking, easy to handle, and has high adhesive strength.

[0149] In the method for producing a pressure-sensitive adhesive of this embodiment, "extrusion" is not limited to the meaning of simultaneous extrusion, but refers to extrusion so as to form an extrudate of uniform composition.

[0150] In the method for producing a pressure-sensitive adhesive of this embodiment, each composition (Composition C, Composition F) is preferably a composition whose adhesive strength has been adjusted to be weak. Specifically, when the adhesive strength of each composition is measured according to the "Method for Measuring Adhesion Strength (Thermoplastic Elastomer, Each Composition, and Each Dry Blend Composition)" described in the Examples below, it is preferably 15.0 N / 10 mm or less, more preferably 14.0 N / 10 mm or less, even more preferably 13.0 N / 10 mm or less, even more preferably 12.0 N / 10 mm or less, even more preferably 10.0 N / 10 mm or less, particularly preferably 5.0 N / 10 mm or less, and even more preferably 1.0 N / 10 mm or less. Furthermore, when the adhesive strength is measured according to the "Method for Measuring Tack Strength" (for the thermoplastic elastomer, each composition, and each dry blend composition) described below, the tack strength is preferably 10.0 N / 5 mmΦ or less, more preferably 8.0 N / 5 mmΦ or less, even more preferably 6.0 N / 5 mmΦ or less, even more preferably 5.0 N / 5 mmΦ or less, even more preferably 3.0 N / 5 mmΦ or less, and particularly preferably 1.0 N / 5 mmΦ or less. Each of the compositions exhibiting such adhesive strength cannot be used alone for pressure-sensitive adhesive applications that require high adhesive strength, but by combining and kneading them in appropriate compositions and amounts, they can exhibit higher adhesive strength than when used alone.

[0151] In a typical method for producing a pressure-sensitive adhesive, for example, when a pressure-sensitive adhesive layer is formed using a composition that exhibits a desired adhesive strength, if this composition is made into pellets and extruded using an extruder, the pellets have such strong adhesive strength that they are prone to blocking and are difficult to handle. Therefore, in the method for producing a pressure-sensitive adhesive of this embodiment, a composition exhibiting a desired adhesive strength is separated into at least two compositions having different compositions (for example, a combination of composition C and composition F), and each is formed into a pellet. By mixing these in a predetermined ratio and extruding them, it is possible to set the pressure-sensitive adhesive so that it has low adhesiveness when in the pellet state but exhibits strong adhesive strength when it is formed into a pressure-sensitive adhesive.

[0152] In the method for producing a pressure-sensitive adhesive of this embodiment, more specifically, the composition ratio and mixing ratio of composition C and composition F can be determined as follows. For example, consider a pressure-sensitive adhesive consisting only of a thermoplastic elastomer and a tackifier, where the composition ratio of all thermoplastic elastomers X to all tackifiers Y in the pressure-sensitive adhesive exhibiting the desired adhesive strength is y:1-y. In composition C, the ratio of all thermoplastic elastomers X to the total amount of all thermoplastic elastomers X and all tackifiers Y is defined as α, and the ratio of all tackifiers Y to the total amount of all thermoplastic elastomers X and all tackifiers Y is defined as (1-α). In composition F, the ratio of all thermoplastic elastomers X to the total amount of all thermoplastic elastomers X and all tackifiers Y is defined as β, and the ratio of all tackifiers Y to the total amount of all thermoplastic elastomers X and all tackifiers Y is defined as (1-β). In this case, when compositions C and F are mixed in a mixing ratio of γ:1-γ, the composition ratio of all thermoplastic elastomers X to all tackifiers Y in the mixture can be written as [(α-β)γ+β]:[1-[(α-β)γ+β)}]. First, α and β are determined so that α and β are as close as possible within the range of weak adhesive strength, and then γ is determined so that the overall composition is y:1-y, thereby determining the compositions of composition C and composition F and the mixing ratio of the two. At this time, the relationship β < y < α holds among α, β, and y. In the pressure-sensitive adhesive, the relationship between the "mixing ratio of the thermoplastic elastomer and the tackifier" and the "tack" is a convex upward curve relationship. Therefore, in the region where the blending amount of the total thermoplastic elastomer X is large or small from the desired composition ratio y, there is a range where the tack decreases. Therefore, by mixing the composition having the composition ratio α different from the desired composition ratio y and the composition having the composition ratio β as described above, it is possible to exhibit a high tack when mixed while suppressing the tack of each composition weakly. Also, in the range where the tack is weak, by making α and β as close as possible, the fluidities of both compositions become close. When the fluidities of both compositions are close, the time until melting in the extruder and the viscosity at the time of melting approach each other, so that they tend to be mixed more uniformly. As a result, the overall composition approaches y:1-y, and it becomes easier to exhibit the desired tack. Also, it becomes difficult for unmelted matter to remain, and the film appearance tends to improve.

[0153] This example utilizes the fact that in a composition showing high tack, the tack can be weakened by changing the ratio of the thermoplastic elastomer and the tackifier. The tacks of composition C and composition F are made low, and the mixing ratio of composition C and composition F is adjusted to design a pressure-sensitive adhesive having a high tack as a whole. The thermoplastic elastomer and the tackifier contained in each composition may of course be different.

[0154] In the pressure-sensitive adhesive of the present embodiment, "components Z other than the thermoplastic elastomer and the tackifier" typified by the plasticizer can also be appropriately blended. At that time, the composition ratios and the mixing ratio can be determined in the same manner as described above.

[0155] Also, when mixing three or more compositions to form a pressure-sensitive adhesive having a desired composition ratio, the composition ratios and the mixing ratio can be determined in the same manner as described above.

[0156] By simultaneously extruding each composition (composition C and composition F) whose composition ratios have been determined as described above using the same extruder, the composition has weak adhesive strength and is easy to handle, and after being kneaded, it can exhibit higher adhesive strength than each composition.

[0157] In the method for producing a pressure-sensitive adhesive of this embodiment, from the viewpoint of obtaining a more uniform pressure-sensitive adhesive, it is preferable that each of the compositions is in particulate form, and that the method includes a dry blending step in which each of the compositions, specifically composition C and composition F, is dry blended before the extrusion step to prepare material G for a pressure-sensitive adhesive.

[0158] In the method for producing a pressure-sensitive adhesive of this embodiment, it is preferable to satisfy the following <Condition (11)>, from the viewpoints of suppressing classification during extrusion molding and making it easier to form a highly uniform pressure-sensitive adhesive when made into a pressure-sensitive adhesive. Furthermore, from the viewpoint of forming a highly uniform pressure-sensitive adhesive, it is preferable that the following <Condition (12)> be satisfied.

[0159] <Condition (11)> The ratio (Wc / Wf) of the average particle mass Wc of composition C to the average particle mass Wf of composition F is preferably 0.4 or more and 2.5 or less, more preferably 0.4 or more and 2.3 or less, even more preferably 0.5 or more and 2.0 or less, and even more preferably 0.6 or more and 1.5 or less.

[0160] <Condition (12)> The ratio of the average particle length Lc of composition C to the average particle length Lf of composition F is preferably 0.6 or more and 1.4 or less, more preferably 0.7 or more and 1.3 or less, even more preferably 0.8 or more and 1.2 or less, and even more preferably 0.9 or more and 1.1 or less. The ratio of the average particle minor diameter lc of composition C to the average particle minor diameter lf of composition F is preferably 0.6 or more and 1.4 or less, more preferably 0.7 or more and 1.3 or less, even more preferably 0.8 or more and 1.2 or less, and even more preferably 0.9 or more and 1.1 or less. The average particle mass, average particle length, and average particle length of the composition can be measured by the methods described in the Examples below.

[0161] From the viewpoint of being more resistant to blocking and having excellent handleability, it is preferable that the adhesive strength of at least one of the compositions is 4.0 N / 10 mm or less when measured according to the "Method for measuring adhesive strength (thermoplastic elastomer, each composition, and each dry blend composition)" described below.

[0162] The mass of the total thermoplastic elastomer in the pressure-sensitive adhesive of this embodiment is preferably 30% by mass or more and 80% by mass or less, from the viewpoint of obtaining a pressure-sensitive adhesive having even better adhesive strength, tackiness, and holding power. The mass of the total tackifier in the pressure-sensitive adhesive is preferably 20% by mass or more and 70% by mass or less, from the viewpoint of obtaining a pressure-sensitive adhesive having even better adhesive strength, tackiness, and holding power.

[0163] When the pressure-sensitive adhesive material of this embodiment is used as a pressure-sensitive adhesive for resealable packaging, it has the advantage that a variety of conditions can be set during extrusion molding to produce a multilayer film. For example, even when the extrusion temperature is set to a generally low temperature of about 120 to 140°C, the dry blend is easily mixed and a uniform adhesive layer with little unevenness in mixing is easily formed. This prevents deterioration of the appearance due to foreign matter resulting from uneven mixing, and also provides the effect of increasing the re-peel strength due to the thermoplastic elastomer and tackifier resin being uniformly mixed in the desired ratio. The pressure-sensitive adhesive material of this embodiment is designed with a focus on ease of mixing during extrusion molding, and the particles are more easily mixed with each other than with conventional compositions, so it is less dependent on the structure of the extruder (screw, etc.) and the settings of the kneading and extrusion conditions, making it easy to produce a multilayer film that exhibits the desired peel strength. On the other hand, when the kneading temperature is set to about 150°C to 230°C, sufficient and uniform mixing can be achieved in a shorter time than with conventional compositions, thereby improving production efficiency. [Example]

[0164] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. The methods for measuring the properties and characteristics of the polymers used in the examples and comparative examples are shown below.

[0165] [Measurement and evaluation methods] ((1): Characteristics of thermoplastic elastomers) <(1-1): Vinyl aromatic monomer unit (styrene) content> A certain amount of thermoplastic elastomer was dissolved in chloroform and measured with an ultraviolet spectrophotometer (Shimadzu Corporation, UV-2450). The content of vinyl aromatic monomer units (styrene) in the thermoplastic elastomer was calculated using a calibration curve based on the peak intensity of the absorption wavelength (262 Nm) attributable to the vinyl aromatic compound component (styrene).

[0166] <(1-2):Weight average molecular weight> The weight average molecular weights of the block copolymers (C), (D-1), (D-2), and (D-3) constituting the thermoplastic elastomer were determined based on the molecular weights of the peaks in the chromatograms using a calibration curve (prepared using the peak molecular weights of the standard polystyrene) obtained from the measurement of commercially available standard polystyrene under the [Measurement Conditions] described below. For the hydrogenated products, the molecular weight of the polymer was measured after hydrogenation. First, the single peak having the lowest peak top molecular weight in the molecular weight range of 20,000 or more and having an area ratio, calculated by peak division described below, of 0.01 or more relative to the total peak area of ​​the thermoplastic elastomer, which is the block copolymer composition, was designated as block copolymer (C), and the peaks in the molecular weight range higher than this were designated as (D-1), (D-2), and (D-3), in order of decreasing molecular weight. The weight average molecular weight of each of the block copolymers (C), (D-1), (D-2), and (D-3) was determined by vertical division to the baseline at the inflection point between each peak of the GPC curve using the system software described below. Here, the inter-peak inflection point (inflection point) of block copolymers (C), (D-1), (D-2), and (D-3) was defined as the lowest vertical point (valley peak) between adjacent peaks. Furthermore, if there were consecutive lowest points, the midpoint was defined as the midpoint. Vertical division was performed using the waveform separation function in the system software described above based on the inflection point, and after division, each weight average molecular weight and area ratio was calculated.

[0167] [Measurement conditions] GPC: ACQUITY APC system (manufactured by Nihon Waters Co., Ltd.) System (measurement and analysis) software: EmpowEr3 Detector: RI Refractive index unit full scale: 500μRIU Output full scale: 2000mV Sampling rate: 10 points / sec Column: ACQUITY APC XT125 (4.6 mm x 150 mm); 1 ACQUITY APC XT200(4.6mm×150mm);1 piece ACQUITY APC XT900(4.6mm×150mm);1 piece ACQUITY APC XT450(4.6mm×150mm);1 piece Solvent: THF Flow rate: 1.0mL / min Concentration: 0.1mg / mL Column temperature: 40°C Injection volume: 20μL

[0168] <(1-3): Weight average molecular weight ratio> The weight-average molecular weight ratios (block copolymer (D-1) / block copolymer (C)), (block copolymer (D-2) / block copolymer (C)), and (block copolymer (D-3) / block copolymer (C)) were calculated from the weight-average molecular weights of block copolymers (C), (D-1), (D-2), and (D-3) determined above.

[0169] <(1-4): Contents of Block Copolymers (C), (D-1), (D-2), and (D-3)> The ratio of the total peak area of ​​the elution curve measured in (1-2) above to the block copolymer (C) The area ratios of (D-1), (D-2), and (D-3) were taken as the contents of block copolymers (C), (D-1), (D-2), and (D-3). The peak having its top at a position 1.5 times or more and less than 2.5 times the weight average molecular weight of the block copolymer (C) was designated as component (D-1), the peak having its top at a position 2.5 times or more and less than 3.4 times the weight average molecular weight of the block copolymer (C) was designated as component (D-2), and the peak having its top at a position 3.4 times or more and less than 4.5 times the weight average molecular weight of the block copolymer (C) was designated as component (D-3). The area ratio, weight average molecular weight, and weight average molecular weight ratio of the block copolymers (D-1), (D-2), and (D-3) were determined by GPC measurement using the above-mentioned apparatus and conditions, followed by vertical division of the GPC curve to the baseline at the inflection points between each peak using the above-mentioned system software. Here, the inflection point between each peak of block copolymers (D-1), (D-2), and (D-3) was defined as the lowest vertical point (valley peak) between adjacent peaks. Furthermore, if there were consecutive lowest points, the midpoint was defined as the midpoint. Using the inflection points, vertical division was performed using the waveform separation function in the system software described above. After division, each weight average molecular weight, each weight average molecular weight ratio, and each area ratio were calculated.

[0170] <(1-5): Average vinyl bond content in conjugated diene monomer unit> Using the thermoplastic elastomer, which is the block copolymer composition before hydrogenation, the average vinyl bond content in the conjugated diene monomer unit was calculated by the Hampton method using an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-230).

[0171] <(1-6): Hydrogenation rate> The total hydrogenation rate of the unsaturated double bonds based on the conjugated diene compound in the block copolymer was measured using a nuclear magnetic resonance (NMR) spectrometer under the following conditions. First, a large amount of methanol was added to the reaction solution after the hydrogenation reaction to precipitate and recover the block copolymer. Next, the block copolymer is extracted with acetone, and the extract is dried under vacuum. 1 This was used as a sample for H-NMR measurement. 1 The conditions for H-NMR measurement are as follows: (Measurement conditions) Measuring equipment: JNM-LA400 (JEOL) Solvent: deuterated chloroform Measurement sample: Samples taken before and after hydrogenation of polymer Sample concentration: 50mg / mL Observation frequency: 400MHZ Chemical shift standard: TMS (tetramethylsilane) Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Measurement temperature: 26℃

[0172] <(1-8): Melt flow rate (MFR)> The MFR of the thermoplastic elastomer was measured at 190°C and a load of 2.16 kg according to condition (d) of ISO standard 1133. The MFR is the mass (g / 10 min) of a thermoplastic elastomer previously placed in a vertical cylinder that flows through a die of constant diameter under a total load of 2.16 kg on a piston in 10 minutes. The MFR values ​​reported herein were measured under these same conditions unless otherwise specified.

[0173] ((2): Measurement of adhesive performance) <(2-1):Method for measuring adhesive strength> [Adhesion strength of thermoplastic elastomer, each composition described below, and each dry blend composition] Thermoplastic elastomers 1 to 2, compositions 1 to 13, and dry blend compositions 1 to 17 were each dissolved in toluene. The obtained toluene solution was applied to a polyester film (thickness: 38 μm) using an applicator, and then the film was left at room temperature for 30 minutes and then in an oven at 70°C for 7 minutes to completely evaporate the toluene, producing a coated film with a coating thickness of 25 μm. The obtained coated film was cut into 15 mm widths, and in accordance with JIS Z0237 "Method 1 for measuring peel adhesion: Method for measuring 180° peel adhesion against test plate," the film was pressed with a roll so that the coated surface was in contact with the stainless steel plate (SUS304), and the peel adhesion was measured 30 minutes after pressing. The peeling speed was 300 mm / min.

[0174] [Initial and resealable peel strength of three-layer film] Three-layer films 1 to 17 were heat-sealed at 150°C, 0.2 MPA, 8 seconds, and a width of 4 mm with the heat seal layer in contact with a polyethylene plate (1 mm thick). After that, peel adhesion was measured at 23°C, 180°C, and a peel speed of 300 mm / min to measure the initial peel strength. The peeled area was then pressed with fingers and resealed three times, after which the peel adhesion was measured again at 23°C, 180°, and a peel speed of 300 mm / min to measure the resealable peel strength.

[0175] <(2-2): Measurement method of tack strength> [Tackiness of Thermoplastic Elastomer, Each Composition, and Each Dry Blend Composition] Thermoplastic elastomers 1 to 2, compositions 1 to 13, and dry blend compositions 1 to 17 were each dissolved in toluene. The resulting toluene solution was applied to a polyester film (thickness: 38 μm) using an applicator, and then the film was left at room temperature for 30 minutes and then in an oven at 70°C for 7 minutes to completely evaporate the toluene, producing a coated film with a thickness of 25 μm. The obtained coated film was cut into a width of 15 mm and placed on the top surface of a 10 g load (cylindrical) of a probe tack tester (NTS-4800 / manufactured by Tester Sangyo Co., Ltd.) with the coated surface facing downward. A 5mm diameter stainless steel cylinder was attached to the coated surface from below for 1 second, lifting off the surface. The cylinder was then peeled off and the peel force was measured. The adhesion and peeling speeds were 10mm / sec.

[0176] ((3): Measurement of average particle length and average particle width) 20 particles of each of the thermoplastic elastomers 1 and 2 and compositions 1 to 13 were randomly selected, and the maximum and minimum diameters of each particle were measured using a vernier caliper. The average maximum diameter of the 20 particles was taken as the average particle length, and the average minimum diameter was taken as the average particle length.

[0177] ((4): Measurement of average particle mass) Twenty particles of each of the thermoplastic elastomers 1 and 2 and compositions 1 to 13 were randomly selected, and the mass of each particle was measured using a precision balance. The average mass of the 20 particles was taken as the average particle mass.

[0178] (5) Evaluation of color tone of thermoplastic elastomer and composition Thermoplastic elastomers 1 to 2 and compositions 1 to 13 were visually observed, and the intensity of yellowness was scored as follows, and the average of the scores from five people was used as the evaluation of color tone. 0 points: No yellowness is felt 1 point: A slightly yellowish color 2 points: The color appears completely yellow

[0179] (6) Evaluation of odor intensity of thermoplastic elastomers, compositions, and three-layer films The thermoplastic elastomers 1 to 2, compositions 1 to 13, and three-layer films 1 to 17 were subjected to a sensory evaluation of odor in an environment of 23°C. The odor intensity was scored as follows, and the average of the scores from the five people was used as the odor intensity evaluation. 0 points: Odorless 1 point: barely detectable smell 2 points: A weak smell that lets you know what it is 3 points: Easily detectable odor 4 points: Strong odor 5 points: Strong odor

[0180] (7): Evaluation of film appearance Three-layer films 1 to 17 were cut into a piece 40 cm wide and 1 m long, and the appearance was visually observed. The samples were rated as ◯ when no small or streak-like defects were visible at first glance, △ when a few defects were visible, and × when defects were visible all over the surface. In addition, the cases where film formation was not possible and evaluation was not possible were marked with "-".

[0181] [Preparation of hydrogenation catalyst] In the examples and comparative examples described below, the hydrogenation catalysts used in producing hydrogenated thermoplastic elastomers were prepared by the following method. A reaction vessel equipped with a stirrer was purged with nitrogen, and 1 L of dried and purified cyclohexane was placed in the vessel. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While thoroughly stirring, an N-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was allowed to react at room temperature for about 3 days, thereby obtaining a hydrogenation catalyst.

[0182] [Preparation of Thermoplastic Elastomer] <Thermoplastic elastomer 1> A 10 L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and purged with nitrogen. 4,480 g of cyclohexane and 128 g of pre-purified styrene were charged, and TMEDA (tetramethylethylenediamine) was added so that the molar ratio relative to the total number of moles of n-butyllithium was 0.28 (0.68 g by mass). Hot water was passed through the jacket to heat the contents to 53°C. Next, a cyclohexane solution containing 1.37 g of n-butyllithium was added to initiate the polymerization of styrene. The liquid temperature rose due to the polymerization of styrene, and 5 minutes after the reaction temperature reached a maximum of 58°C, 672 g of 1,3-butadiene was added to continue the polymerization. Three minutes after the reaction temperature reached a maximum of 88°C, tetraethoxysilane was added as a coupling agent so that the molar ratio relative to the total number of moles of n-butyllithium was 0.086 (0.31 g by mass), and the coupling reaction was carried out for 20 minutes. The average reaction temperature during this period was 71°C. 20 minutes after the addition of the coupling agent, 0.4 g of methanol was added to quench the reaction, thereby obtaining a block copolymer composition. Furthermore, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer composition in an amount of 50 ppm (Ti basis) per 100 parts by mass of the block copolymer composition, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 87°C. The hydrogenation rate of the resulting block copolymer composition was 43.2% by mass. To the obtained block copolymer composition solution, 0.30 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and 0.03 parts by mass of 2,4-bis(octylthiomethyl)-6-methylphenol were added relative to 100 parts by mass of the block copolymer composition, and the mixture was thoroughly mixed. Thereafter, the solvent was removed by heating, and the mixture was pelletized to obtain a thermoplastic elastomer 1 containing the block copolymers (C), (D-1), (D-2), and (D-3). The obtained thermoplastic elastomer 1 had a vinyl aromatic monomer unit content of 16.3% by mass, and an average vinyl bond content of the conjugated diene monomer units of 32.5% by mass. Other physical properties of the obtained thermoplastic elastomer 1 are shown in Table 1.

[0183] <Thermoplastic elastomer 2> A 10 L stainless steel autoclave equipped with a stirrer and a jacket was cleaned, dried, and purged with nitrogen. 4480 g of cyclohexane and 240 g of pre-purified styrene were charged. TMEDA (tetramethylethylenediamine) was added so that the molar ratio relative to the total number of moles of n-butyllithium was 0.33 (1.04 g by mass). Warm water was passed through the jacket to heat the contents to 53 °C. Next, a cyclohexane solution containing 1.79 g of n-butyllithium was added to initiate the polymerization of styrene. The liquid temperature rose due to the polymerization of styrene, and 5 minutes after the reaction temperature reached a maximum of 58 °C, 560 g of 1,3-butadiene was added to continue the polymerization. 3 minutes after the reaction temperature reached a maximum of 88 °C, ethyl benzoate was added as a coupling agent so that the molar ratio relative to the total number of moles of n-butyllithium was 0.150 (0.35 g by mass). The coupling reaction was allowed to proceed for 15 minutes. The average reaction temperature during this period was 71 °C. 15 minutes after the addition of the coupling agent, 0.4 g of methanol was added to quench the reaction, thereby obtaining a block copolymer composition. Furthermore, the hydrogenation catalyst prepared as described above was added to the resulting block copolymer composition in an amount of 50 ppm (Ti basis) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 87° C. The hydrogenation rate of the resulting block copolymer composition was 50.3% by mass. To the resulting block copolymer solution, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added per 100 parts by mass of the block copolymer, and the mixture was thoroughly mixed. The solvent was then removed by heating, and the mixture was pelletized to obtain a thermoplastic elastomer 2 containing block copolymers (C) and (D-1). The obtained thermoplastic elastomer 2 had a vinyl aromatic monomer unit content of 29.7% by mass, and an average vinyl bond content of the conjugated diene monomer units of 40.2% by mass. Other physical properties of the obtained thermoplastic elastomer 2 are shown in Table 1.

[0184] [Table 1]

[0185] The method for preparing the composition constituting the pressure-sensitive adhesive material is described below. The tackifiers used in the compositions constituting the pressure-sensitive adhesive materials (hereinafter referred to as compositions) are shown in Table 2 below.

[0186] [Table 2]

[0187] [Preparation of Composition Constituting Pressure-Sensitive Adhesive Material] [Manufacturing Examples 1-1 to 1-13] (Composition 1) Using a twin-screw extruder, a mixture was obtained by kneading at 160°C thermoplastic elastomer 1 (233 parts by mass), tackifier Alcon P100 (100 parts by mass) manufactured by Arakawa Chemical Industries, Ltd., and antioxidant Irganox #1010 (0.5 parts by mass) manufactured by Ciba Specialty Chemicals. The resulting kneaded product was extruded into water, formed into pellets using an underwater cutter, and dried in a continuous dryer to obtain (Composition 1). Other physical properties of (Composition 1) are shown in Table 3 below.

[0188] (Composition 2) Composition 2 was obtained in the same manner as in Composition 1, except that Kolon's Scolez SU420 (100 parts by mass) was used as the tackifier. Other physical properties of (Composition 2) are shown in Table 3 below.

[0189] (Composition 3) Composition 3 was obtained in the same manner as in Composition 1, except that YS Resin PX1150N (100 parts by mass) manufactured by Yasuhara Chemical Co., Ltd. was used as the tackifier. Other physical properties of (Composition 3) are shown in Table 3 below.

[0190] (Composition 4) Composition 4 was obtained in the same manner as in Composition 1, except that Arkon P140 (100 parts by mass) manufactured by Arakawa Chemical Industries, Ltd. was used as the tackifier. Other physical properties of (Composition 4) are shown in Table 3 below.

[0191] (Composition 5) Composition 5 was obtained in the same manner as in Composition 1, except that Thermoplastic Elastomer 2 (233 parts by mass) was used as the thermoplastic elastomer. Other physical properties of (Composition 5) are shown in Table 3 below.

[0192] (Composition 6) Using a twin-screw extruder, a mixture was obtained by kneading at 160°C Thermoplastic elastomer 1 (100 parts by mass), Arakawa Chemical Industries' Alcon P100 (233 parts by mass) as a tackifier, and Ciba Specialty Chemicals' Irganox #1010 (0.5 parts by mass) as an antioxidant. The resulting kneaded product was extruded into water, formed into pellets using an underwater cutter, and dried in a continuous dryer to obtain (Composition 6). Other physical properties of (Composition 6) are shown in Table 3 below.

[0193] (Composition 7) Composition 7 was obtained in the same manner as in Composition 6, except that Kolon's Scolez SU420 (100 parts by mass) was used as the tackifier. Other physical properties of (Composition 7) are shown in Table 3 below.

[0194] (Composition 8) Composition 8 was obtained in the same manner as Composition 6, except that YS Resin PX1150N (100 parts by mass) manufactured by Yasuhara Chemical Co., Ltd. was used as the tackifier. Other physical properties of (Composition 8) are shown in Table 4 below.

[0195] (Composition 9) Composition 9 was obtained in the same manner as in Composition 6, except that Arkon P140 (100 parts by mass) manufactured by Arakawa Chemical Industries, Ltd. was used as the tackifier. Other physical properties of (Composition 9) are shown in Table 4 below.

[0196] (Composition 10) Composition 10 was obtained in the same manner as in Composition 7, except that Thermoplastic Elastomer 2 (233 parts by mass) was used as the thermoplastic elastomer. Other physical properties of (Composition 10) are shown in Table 4 below.

[0197] (Composition 11) Composition 11 was obtained in the same manner as in Composition 10, except that YS Resin PX1150N (100 parts by mass) manufactured by Yasuhara Chemical Co., Ltd. was used as the tackifier. Other physical properties of (Composition 11) are shown in Table 4 below.

[0198] (Composition 12) Using a twin-screw extruder, a mixture was obtained by kneading at 160°C thermoplastic elastomer 1 (266 parts by mass), tackifier Alcon P100 (67 parts by mass) manufactured by Arakawa Chemical Industries, Ltd., and antioxidant Irganox #1010 (0.5 parts by mass) manufactured by Ciba Specialty Chemicals. The resulting kneaded product was extruded into water, formed into pellets using an underwater cutter, and dried in a continuous dryer to obtain (Composition 12). Other physical properties of (Composition 12) are shown in Table 4 below.

[0199] (Composition 13) Using a twin-screw extruder, a mixture was obtained by kneading at 160°C thermoplastic elastomer 1 (200 parts by mass), Arakawa Chemical Industries' Alcon P100 (133 parts by mass) as a tackifier, and Ciba Specialty Chemicals' Irganox #1010 (0.5 parts by mass) as an antioxidant. The resulting kneaded product was extruded into water, formed into pellets using an underwater cutter, and dried in a continuous dryer to obtain (Composition 13). Other physical properties of (Composition 13) are shown in Table 4 below.

[0200] The compositions and physical properties of the compositions prepared as described above, which contained a thermoplastic elastomer and a tackifier, are shown in Tables 3 and 4 below.

[0201] [Table 3]

[0202] [Table 4]

[0203] [Preparation of Pressure-Sensitive Adhesive Material (Dry Blend Composition)] [Example 2-1 8, Reference Examples 2-9, Example 2- 10, Comparative Examples 2-1 to 2-7] The pressure-sensitive adhesive materials were Composition C and Composition F as shown in Tables 5 and 6 below. was prepared by combining Compositions C and F were selected from compositions 1 to 13.

[0204] (Dry Blend Composition 1) Dry blend composition 1 was prepared by dry blending composition 1 (100 parts by mass) as composition C and composition 6 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 1 are shown in Table 5 below.

[0205] (Dry Blend Composition 2) Dry blend composition 2 was prepared by dry blending composition 2 (100 parts by mass) as composition C and composition 7 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 2 are shown in Table 5 below.

[0206] (Dry Blend Composition 3) Dry blend composition 3 was prepared by dry blending composition 3 (100 parts by mass) as composition C and composition 8 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 3 are shown in Table 5 below.

[0207] (Dry Blend Composition 4) Dry blend composition 4 was prepared by dry blending composition 1 (100 parts by mass) as composition C and composition 7 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 4 are shown in Table 5 below.

[0208] (Dry Blend Composition 5) Dry blend composition 5 was prepared by dry blending composition 4 (100 parts by mass) as composition C and composition 9 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 5 are shown in Table 5 below.

[0209] (Dry Blend Composition 6) Dry blend composition 6 was prepared by dry blending composition 5 (100 parts by mass) as composition C and composition 10 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 6 are shown in Table 5 below.

[0210] (Dry Blend Composition 7) Dry blend composition 7 was prepared by dry blending composition 1 (100 parts by mass) as composition C and composition 10 (100 parts by mass) as composition F. Other physical properties of Dry Blend Composition 7 are shown in Table 5 below.

[0211] (Dry Blend Composition 8) Dry blend composition 8 was prepared by dry blending composition 12 (80 parts by mass) as composition C and composition 7 (120 parts by mass) as composition F. Other physical properties of Dry Blend Composition 8 are shown in Table 5 below.

[0212] (Dry Blend Composition 9) Dry blend composition 9 was prepared by dry blending thermoplastic elastomer 2 (100 parts by mass) and composition 8 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 9 are shown in Table 5 below. In Table 5, to facilitate comparison with other dry blend compositions, the thermoplastic elastomer was used to calculate the physical properties of composition C. For example, the average particle mass of thermoplastic elastomer 2 was calculated as Wc.

[0213] (Dry Blend Composition 10) Dry blend composition 10 was prepared by dry blending composition 5 (100 parts by mass) as composition C and composition 8 (100 parts by mass) as composition F. Other physical properties of dry blend composition 10 are shown in Table 5 below.

[0214] (Dry Blend Composition 11) Dry blend composition 11 was prepared by dry blending thermoplastic elastomer 1 (100 parts by mass) and composition 6 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 11 are shown in Table 6 below.

[0215] (Dry Blend Composition 12) Dry blend composition 12 was prepared by dry blending thermoplastic elastomer 1 (100 parts by mass) and composition 7 (250 parts by weight) as composition F. Other physical properties of Dry Blend Composition 12 are shown in Table 6 below.

[0216] (Dry Blend Composition 13) Dry blend composition 13 was prepared by dry blending thermoplastic elastomer 1 (100 parts by mass) and composition 8 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 13 are shown in Table 6 below.

[0217] (Dry Blend Composition 14) Dry blend composition 14 was prepared by dry blending thermoplastic elastomer 1 (100 parts by mass) and composition 9 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 14 are shown in Table 6 below.

[0218] (Dry Blend Composition 15) Dry blend composition 15 was prepared by dry blending thermoplastic elastomer 2 (100 parts by mass) and composition 7 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 15 are shown in Table 6 below.

[0219] (Dry Blend Composition 16) Dry blend composition 16 was prepared by dry blending thermoplastic elastomer 2 (100 parts by mass) and composition 11 (250 parts by mass) as composition F. Other physical properties of Dry Blend Composition 16 are shown in Table 6 below.

[0220] (Dry Blend Composition 17) Dry blend composition 17 was prepared by dry blending composition 13 (133 parts by mass) as composition C and composition 6 (67 parts by mass) as composition F. Other physical properties of Dry Blend Composition 17 are shown in Table 6 below.

[0221] [Production of three-layer film] [Example 3-1 8, Reference Examples 3-9, Example 3- 10, Comparative Examples 3-1 to 3-7] (Three-layer film 1) Dry blend composition 1 was used as a pressure-sensitive adhesive layer, and polypropylene (manufactured by SunAllomer Co., Ltd.) Product name: PC684S, MFR (230°C, 2.16 kg load) = 7.5 g / 10 min) The base layer is made of low-density polyethylene (manufactured by Asahi Kasei Corporation, product name "Suntech L2340", M FR (190°C, 2.16 kg load) = 3.8 g / 10 min)) as a heat seal layer, Using each, a T-die co-extrusion method was used so that the pressure-sensitive adhesive layer was the center layer of the three layers. The layers were integrated and co-extruded to produce a three-layer film 1. The extruder temperature setting was 210°C for the polypropylene layer and 170°C for the low-density polyethylene layer. The temperature of the pressure-sensitive adhesive layer was 130°C. Other physical properties of Three-Layer Film 1 are shown in Table 7 below.

[0222] (Three-layer film 2) Three-layer film 2 was obtained in the same manner as three-layer film 1, except that dry blend composition 2 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 2 are shown in Table 7 below.

[0223] (Three-layer film 3) Three-layer film 3 was obtained in the same manner as three-layer film 1, except that dry blend composition 3 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 3 are shown in Table 7 below.

[0224] (Three-layer film 4) Three-layer film 4 was obtained in the same manner as three-layer film 1, except that dry blend composition 4 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 4 are shown in Table 7 below.

[0225] (Three-layer film 5) Three-layer film 5 was obtained in the same manner as three-layer film 1, except that dry blend composition 5 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 5 are shown in Table 7 below.

[0226] (Three-layer film 6) Three-layer film 6 was obtained in the same manner as three-layer film 1, except that dry blend composition 6 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 6 are shown in Table 7 below.

[0227] (Three-layer film 7) Three-layer film 7 was obtained in the same manner as three-layer film 1, except that dry blend composition 7 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 7 are shown in Table 7 below.

[0228] (Three-layer film 8) Three-layer film 8 was obtained in the same manner as three-layer film 1, except that dry blend composition 8 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 8 are shown in Table 7 below.

[0229] (Three-layer film 9) Three-layer film 9 was obtained in the same manner as three-layer film 1, except that dry blend composition 9 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of Three-Layer Film 9 are shown in Table 7 below.

[0230] (Three-layer film 10) Three-layer film 10 was obtained in the same manner as three-layer film 1, except that dry blend composition 10 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 10 are shown in Table 7 below.

[0231] (Three-layer film 11) Three-layer film 11 was obtained in the same manner as three-layer film 1, except that dry blend composition 11 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 11 are shown in Table 8 below.

[0232] (Three-layer film 12) Three-layer film 12 was obtained in the same manner as three-layer film 1, except that dry blend composition 12 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 12 are shown in Table 8 below.

[0233] (Three-layer film 13) Three-layer film 13 was obtained in the same manner as Three-layer film 1, except that Dry Blend Composition 13 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 13 are shown in Table 8 below.

[0234] (Three-layer film 14) Three-layer film 14 was obtained in the same manner as Three-layer film 1, except that Dry Blend Composition 14 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 14 are shown in Table 8 below.

[0235] (Three-layer film 15) Three-layer film 15 was obtained in the same manner as Three-layer film 1, except that Dry Blend Composition 15 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 15 are shown in Table 8 below.

[0236] (Three-layer film 16) Three-layer film 16 was obtained in the same manner as Three-layer film 1, except that dry blend composition 16 was used as the material for the pressure-sensitive adhesive layer. Other physical properties of the three-layer film 16 are shown in Table 8 below.

[0237] (Three-layer film 17) An attempt was made to carry out the same operations as in the three-layer film 1, except that dry blend composition 17 was used as the material for the pressure-sensitive adhesive layer. However, due to the strong adhesive strength of composition 13, blocking occurred and it was not possible to form a film, and three-layer film 17 was not obtained.

[0238] [Examples 2-1 to 2- 8. Reference Examples 2-9. Examples 2-10), [Comparative Examples 2-1 to 2-7] (Dry Blend Composition) The composition, physical properties, and characteristic values ​​of the dry blend compositions prepared as described above are shown in Tables 5 and 6 below.

[0239] [Table 5]

[0240] [Table 6]

[0241] [Example 3-1 to 3-8, Reference Examples 3-9, Examples 3-10), [Comparative Examples 3-1 to 3-7] The structure, properties and evaluation of the three-layer film prepared as described above are shown in Tables 7 and 8 below. Shown below.

[0242] [Table 7]

[0243] [Table 8]

[0244] Comparing the results of Examples 3-1 to 3-7 with those of Comparative Examples 3-1 to 3-6, it was found that when the compositions of Production Examples 1-1 to 1-5 (Compositions 1 to 5) were used, the appearance of the extruded film was significantly improved compared to when a thermoplastic elastomer alone or a composition containing an excessively high proportion of thermoplastic elastomer was used. It was also found that the resealing peel strength also tended to improve. The extrusion conditions for the pressure-sensitive adhesive layer used in the examples, 130°C, were lower than typical extrusion temperatures and were difficult conditions that made mixing difficult. In the prior art Comparative Examples 3-1 to 3-6, the ratio of the MFR values ​​of the two types of particles was not within an appropriate range, which is thought to be why the particles were not sufficiently mixed. On the other hand, the particles contained in the dry blend composition, which is a pressure-sensitive adhesive material of the present invention, were more easily mixed because the ratio of the MFR values ​​of the two types of particles was within an appropriate range. As a result, there was no deterioration in appearance due to foreign matter resulting from uneven mixing, and the composition was more uniform throughout and had the expected mixing ratio, resulting in improved resealing strength. These results demonstrate that the mixability of the particles contained in the dry blend composition, which is a material for pressure-sensitive adhesives of the present invention, is essentially improved. For example, sufficient mixing is possible even when using an extruder with lower mixing capacity. Because the mixing capacity of an extruder varies greatly depending on the equipment used, the type of screw, etc., improved mixability allows the material for pressure-sensitive adhesives of the present invention to be used with a wide range of equipment, making it highly industrially useful. Furthermore, compared to extrusion conditions at 130°C, extrusion conditions such as 150°C to 230°C, which tend to improve mixability, are thought to enable sufficient mixing in a shorter time than conventional techniques, leading to improved throughput and high usefulness.

[0245] Manufacturing Examples 1-1, 1-2, 1-4, 1-5, 1-6, 1-7, 1-9, 1-10, 1-1 From a comparison of the results of 2 and 1-13 with those of Preparation Examples 1-3, 1-8, and 1-11, 1, 1-2, 1-4, 1-5, 1-6, 1-7, 1-9, 1-10, 1-12, 1-13 When using this composition, adhesives other than hydrogenated hydrocarbon resins and / or their derivatives may be used. It was found that the appearance and odor were better than when the additive resin was used. In addition, the results of Examples 3-1, 3-2, and 3-4, and Examples 3-3, 3-5, Reference example Comparison of the results of 3-9, 3-10 and Comparative Examples 3-3, 3-4, and 3-6 revealed that when the compositions of Production Examples 1-1, 1-2, 1-4, 1-5, 1-6, 1-7, 1-9, and 1-10 were used, the odor of the extruded film tended to be improved and the resealing peel strength also tended to be improved compared to when a tackifier resin with a softening point higher than 130°C or a tackifier resin other than a hydrogenated hydrocarbon resin and / or its derivative was used.

[0246] Composition 13 of Production Example 1-13 had such strong adhesive and tacky strength that the particles easily stuck together, causing blocking. Furthermore, dry blend composition 17 of Comparative Example 2-7, which used composition 13, also experienced blocking. Attempts were made to break up the blocking and form a film, but the particles re-adhered to each other in the extruder hopper, making it impossible to feed the particles and resulting in failure to form a film. This demonstrates that using the thermoplastic elastomer ratio specified in the present invention reduces blocking and makes handling easier. [Industrial Applicability]

[0247] The pressure-sensitive adhesive composition of the present invention has industrial applicability as a packaging means for cosmetics or sanitary products that are repeatedly opened and resealed each time they are used, or as a material for the adhesive layer of packaging materials for foods, medicines, and the like in quantities that cannot be consumed in one go.

Claims

1. A pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, comprising: a composition C comprising at least one thermoplastic elastomer A and at least one tackifier B, which are in the form of integrated particles; A composition F comprising at least one thermoplastic elastomer D and at least one tackifier E, which are in the form of integrated particles; Contains the thermoplastic elastomer A includes a block copolymer (C) having a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, the block copolymer (C) having one polymer block (A), and the content of the block copolymer (C) in the thermoplastic elastomer A is 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D includes a block copolymer (F) having a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, the block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition F satisfies the following condition (2): the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive material (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as x; In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, When the mass ratio of the total thermoplastic elastomers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) to the total amount of the total thermoplastic elastomers and the total tackifiers in the composition F is defined as β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is greater than the adhesive strength of composition C having the ratio α and greater than the adhesive strength of composition F having the ratio β; The following formula (1), and the following conditions (13), (5), and (6) are satisfied: the ratio of the blending amount of the composition C to the blending amount of the composition F (blending mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β<x<α (1) <Condition (2)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less. <Condition (13)> The ratio of the MFR value of the composition F to the MFR value of the composition C is 10 or more and 100 or less. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is equal to or greater than 0.4 and equal to or less than 2.

5. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is equal to or greater than 0.6 and equal to or less than 1.

4.

2. 2. The pressure-sensitive adhesive material according to claim 1, wherein the composition C further contains a tackifier B and satisfies the following condition (1): <Condition (1)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and not more than 3.

0.

3. A pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, comprising: At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: At least one thermoplastic elastomer D and at least one tackifier E; and Composition F, which comprises: Contains the thermoplastic elastomer A includes a block copolymer (C) having a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, the block copolymer (C) having one polymer block (A), and the content of the block copolymer (C) in the thermoplastic elastomer A is 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D includes a block copolymer (F) having a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, the block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition C satisfies the following condition (1): The composition F satisfies the following condition (2): the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive material (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as x; In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, When the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the composition F (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is greater than the adhesive strength of composition C having the ratio α and greater than the adhesive strength of composition F having the ratio β; The following formula (1), the following condition (5), and the following condition (6) are satisfied, the ratio of the blending amount of the composition C to the blending amount of the composition F (blending mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β<x<α (1) <Condition (1)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and not more than 3.

0. <Condition (2)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is equal to or greater than 0.4 and equal to or less than 2.

5. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is equal to or greater than 0.6 and equal to or less than 1.

4.

4. A pressure-sensitive adhesive material used for a pressure-sensitive adhesive contained in a multilayer film for resealable packaging, comprising: At least one thermoplastic elastomer A and at least one tackifier B; and Composition C, which comprises the following in a united, particulate form: A composition F comprising at least one thermoplastic elastomer D and at least one tackifier E, which are in the form of integrated particles; Contains the thermoplastic elastomer A includes a block copolymer (C) having a polymer block (A) mainly composed of vinyl aromatic monomer units and a polymer block (B) mainly composed of conjugated diene monomer units, the block copolymer (C) having one polymer block (A), and the content of the block copolymer (C) in the thermoplastic elastomer A is 60% by mass or more and 80% by mass or less; the thermoplastic elastomer D includes a block copolymer (F) having a polymer block (D) mainly composed of a vinyl aromatic monomer unit and a polymer block (E) mainly composed of a conjugated diene monomer unit, the block copolymer (F) having one polymer block (D), and the content of the block copolymer (F) in the thermoplastic elastomer D is 60% by mass or more and 80% by mass or less; the tackifier B and the tackifier E are at least one selected from the group consisting of aromatic petroleum hydrocarbon resins (C9 resins), hydrogenated products of the aromatic petroleum hydrocarbon resins (C9 resins) and / or derivatives thereof, aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins), hydrogenated products of the aromatic-modified alicyclic hydrocarbon resins (DCPD-C9 resins) and / or derivatives thereof, terpene resins, and hydrogenated products of the terpene resins and / or derivatives thereof; The composition C satisfies the following condition (3): The composition F satisfies the following condition (4): In the material for pressure-sensitive adhesives, of total thermoplastic elastomer relative to the total amount of all thermoplastic elastomers and all tackifiers The mass ratio (total thermoplastic elastomer / total thermoplastic elastomer+total tackifier) ​​is x, In the composition C, relative to the total amount of all thermoplastic elastomers and all tackifiers, The mass ratio of the total thermoplastic elastomers (total thermoplastic elastomers / total thermoplastic elastomers + total tackifiers) is defined as α, In the composition F, relative to the total amount of all thermoplastic elastomers and all tackifiers, When the mass ratio of the total thermoplastic elastomer (total thermoplastic elastomer / total thermoplastic elastomer+total tackifier) ​​is β, The adhesive strength of the pressure-sensitive adhesive material having the ratio x is greater than the adhesive strength of composition C having the ratio α and greater than the adhesive strength of composition F having the ratio β; The following formula (1), the following condition (5), and the following condition (6) are satisfied, the ratio of the blending amount of the composition C to the blending amount of the composition F (blending mass ratio; C / F) is 0.45 or more and 2.00 or less; Material for pressure-sensitive adhesives. β<x<α (1) <Condition (3)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition C is More than 60% by mass and less than 80% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition C is It is more than 20% by mass and less than 40% by mass. <Condition (4)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition F is More than 20% by mass and less than 40% by mass, The ratio of the mass of the total tackifier to the mass of the entire composition F is It is more than 60% by mass and less than 80% by mass. <Condition (5)> The ratio of the average particle mass Wc of the composition C to the average particle mass Wf of the composition F (Wc / Wf) is equal to or greater than 0.4 and equal to or less than 2.

5. <Condition (6)> The ratio of the average particle length Lc of the composition C to the average particle length Lf of the composition F (Lc / Lf) is 0.6 or more and 1.4 or less, The ratio of the average particle minor diameter lc of the composition C to the average particle minor diameter lf of the composition F (lc / lf) is equal to or greater than 0.6 and equal to or less than 1.

4.

5. The tackifier B and the tackifier E are 5. The pressure-sensitive adhesive material according to claim 1, which is a hydrogenated hydrocarbon resin and / or a derivative thereof having a softening point of 130°C or lower.

6. The tackifier B or the tackifier E is A hydrogenated aromatic petroleum hydrocarbon resin (C9 resin) and / or a derivative thereof, The material for pressure-sensitive adhesives according to any one of claims 1 to 4.

7. The tackifier B or the tackifier E is A hydrogenated product of an aromatic modified alicyclic hydrocarbon resin (DCPD-C9 resin) and / or a derivative thereof, The material for pressure-sensitive adhesives according to any one of claims 1 to 4.

8. the tackifier B is a hydrogenated product of an aromatic petroleum hydrocarbon resin (C9 resin) and / or a derivative thereof, The tackifier E is a hydrogenated product of an aromatic modified alicyclic hydrocarbon resin (DCPD-C9 resin) and / or a derivative thereof. The material for pressure-sensitive adhesives according to any one of claims 1 to 4.

9. a composition C in the form of particles, comprising at least one thermoplastic elastomer A and at least one tackifier B; A composition F in particulate form containing at least one thermoplastic elastomer D and at least one tackifier E; The method includes an extrusion step of extruding the material for pressure-sensitive adhesives according to any one of claims 1 to 4, which contains:

1. A method for producing a pressure-sensitive adhesive contained in a multilayer resealable packaging film, comprising: The composition C satisfies the following condition (7): The composition F satisfies the following condition (8): In the extrusion step, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as y; In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, In the composition F, when the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the pressure-sensitive adhesive having a ratio of y is greater than the adhesive strength of composition C having a ratio of α, and greater than the adhesive strength of composition F having a ratio of β; Satisfies the following formula (2): A method for producing a pressure-sensitive adhesive. β<y<α (2) <Condition (7)> In the composition C, the mass ratio of the total thermoplastic elastomer to the total tackifier is more than 1.5 and not more than 3.

0. <Condition (8)> In the composition F, the mass ratio of the total tackifier to the total thermoplastic elastomer is more than 1.5 and 3.0 or less.

10. a composition C in the form of particles, comprising at least one thermoplastic elastomer A and at least one tackifier B; A composition F in particulate form containing at least one thermoplastic elastomer D and at least one tackifier E; The method includes an extrusion step of extruding the material for pressure-sensitive adhesives according to any one of claims 1 to 4, which contains:

1. A method for producing a pressure-sensitive adhesive contained in a multilayer resealable packaging film, comprising: The composition C satisfies the following condition (9): The composition F satisfies the following condition (10): In the extrusion step, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers in the pressure-sensitive adhesive (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as y; In the composition C, the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is defined as α, In the composition F, when the mass ratio of all thermoplastic elastomers to the total amount of all thermoplastic elastomers and all tackifiers (total thermoplastic elastomers / total thermoplastic elastomers+total tackifiers) is β, The adhesive strength of the pressure-sensitive adhesive having a ratio of y is greater than the adhesive strength of composition C having a ratio of α; The adhesive strength is greater than that of composition F, whose ratio is β, Satisfies the following formula (2): A method for producing a pressure-sensitive adhesive. β<y<α (2) <Condition (9)> the ratio of the mass of the total thermoplastic elastomer to the total mass of the composition C is more than 60 mass% and less than 80 mass%, The ratio of the mass of all tackifiers to the total mass of the composition C is more than 20 mass % and less than 40 mass %. <Condition (10)> The ratio of the mass of the total thermoplastic elastomer to the mass of the entire composition F is more than 20% by mass and less than 40% by mass, The ratio of the mass of all tackifiers to the total mass of the composition F is more than 60 mass % and less than 80 mass %.

11. The composition C and the composition F, A dry blending step of dry-blending the compositions to prepare a material G for a pressure-sensitive adhesive is included prior to the extrusion step. A method for producing the pressure-sensitive adhesive according to claim 9 or 10.

12. A pressure-sensitive adhesive comprising the material for pressure-sensitive adhesives according to any one of claims 1 to 8.

13. A multilayer film comprising the pressure-sensitive adhesive of claim 12.

14. A package comprising the multilayer film of claim 13.

Images