JP7135400B2 - Laminate with adhesive layer - Google Patents

Description

The present invention is a laminate having an adhesive layer (so-called adhesive sheet) used exclusively for fixing automotive assembly wires (hereinafter referred to as "wire harness") to a molded ceiling (headlining, rooflining).

In the automobile assembly line, in order to reduce the number of man-hours required, it is used as a component (unit, assembly, assembly) that is combined with a wire harness pre-fixed to the back side of molded automobile parts such as headlinings, bumpers, and door trims. are being supplied.

Conventionally, wire harnesses are fixed to the back side of the headlining by a method of fixing with a hot-melt adhesive, a method of fixing with staples (U-shaped nails, staples), and the like. However, in the case of hot-melt adhesives, a special tool (such as a glue gun) is used to melt the adhesive at a high temperature, and then the wire harness is fixed to the headlining. There was a possibility that it would be lost. Moreover, since it takes time for the melted adhesive to solidify, there is a problem of poor working efficiency.

On the other hand, in the case of staples, since the needles are pierced into the headlining, there is a risk that the staples will penetrate to the opposite side, and there is a problem that the work requires skill.

Therefore, a method of fixing the wire harness to the back side of the headlining using an adhesive sheet has been proposed. As the adhesive sheet, an adhesive sheet having a substrate made of a soft metal foil and an adhesive layer provided on the substrate has been proposed (see Patent Document 1).

However, in the fixing method using the adhesive sheet having the base material made of the soft metal foil and the adhesive provided on the base material, for example, a wire harness having a large outer diameter or a plurality of wire harnesses is used. When fixing with the adhesive sheet, or when fixing the wire harness along the uneven shape of the headlining, the adhesive sheet (metal foil base material of the adhesive sheet) is attached by crimping the adhesive sheet. However, there was a problem that it was easily torn and torn.

In addition, headlinings are often made of polyolefin or polyester materials, and in some cases are made of raised non-woven fabric, and are generally difficult to adhere to. As a result, the adhesive sheet tends to have insufficient adhesion to the headlining, and when the assembly with the wire harness fixed to the headlining is transported to an automobile assembly plant, there is a problem that the wire harness comes off from the headlining. .

In recent years, automobile manufacturers have been actively working on various environmental issues, such as preventing global warming, improving the air quality, and building a recycling-oriented society, and are promoting the production of automobiles that take into account the environment inside the cabin. The Japan Automobile Manufacturers Association has established a method for testing the amount of volatile organic compounds (hereinafter referred to as VOC) emitted from inside a vehicle and a voluntary approach to reduce the amount of VOC emitted from inside a vehicle. In recent years, from the point of view of such environmental considerations, there has been a demand for reducing the amount of 13 volatile organic compounds, including toluene, emitted. A large amount of toluene is used as a diluting solvent in the pressure-sensitive adhesive used in the pressure-sensitive adhesive sheet, and there is a problem that some toluene remains even after the toluene is dried during the production of the pressure-sensitive adhesive sheet.

JP 2006-96856

The problem to be solved by the present invention is that the pressure-sensitive adhesive sheet has a level of strength that does not easily tear during application and excellent adhesion to the headlining without substantially using an aromatic volatile organic compound as a solvent for the pressure-sensitive adhesive. An object of the present invention is to provide a laminate (a so-called adhesive sheet) having an adhesive layer having both strength and peeling resistance.

The present inventors have proposed a laminate having a base laminate material in which a polyolefin resin film and a soft metal foil are laminated, and an adhesive layer containing a styrene-isoprene block copolymer and a hydrocarbon resin, wherein the adhesive layer contains a solvent The inventors have found that the above problems can be solved by providing a laminate that does not substantially use aromatic volatile organic compounds as.

Since the laminate of the present invention does not use an aromatic volatile organic compound as a solvent in the pressure-sensitive adhesive to be used, the amount of the aromatic volatile organic compound emitted in the space inside the automobile can be significantly reduced. It can be used exclusively for fixing the wire harness to the headlining because it can be used for fixing the wire harness to the headlining because it can achieve a level of strength that does not easily tear when the laminate is attached, excellent adhesion to the headlining, and peeling resistance. can. Moreover, the assembly of the wire harness and the headlining fixed by the laminate of the present invention is less likely to come off during the transportation process and can be suitably supplied.

It is a schematic diagram of a method for measuring the cutting strength of a laminate. It is a schematic diagram of the method to evaluate the constant-load peelability of a laminate. It is a schematic diagram of a method for measuring the adhesive strength of a laminate. FIG. 3 is a schematic diagram of a method for evaluating the laminating work suitability of a laminate.

The laminate of the present invention is a pressure-sensitive adhesive sheet comprising a substrate obtained by laminating a polyolefin resin film and a soft metal foil, and a pressure-sensitive adhesive layer provided on at least one side of the substrate directly or via another layer. , wherein the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a styrene-isoprene block copolymer and a hydrocarbon resin and substantially free of aromatic volatile organic compounds as a solvent. be. Moreover, it is used exclusively for the purpose of fixing the wire harness to the headlining.

<Base material>
The substrate constituting the laminate of the present invention is a substrate obtained by laminating a polyolefin resin film and a soft metal foil.

(resin film)
Examples of the polyolefin resin film include those using polyethylene and/or polypropylene. Either a single-layer film or a multi-layer film can be suitably used.

As the polyolefin resin film, a polyethylene film can be suitably used for the purpose of increasing the strength of the base material without impairing the flexibility, and the tear resistance is improved without impairing the peeling resistance of the headlining. can be done.

As the polyolefin-based resin film, a polypropylene film can be suitably used for the purpose of greatly increasing the strength of the base material without significantly impairing flexibility. can be greatly improved.

As the polyolefin-based resin film, a multi-layer film in which polyethylene and polypropylene are combined can be suitably used for the purpose of increasing the strength of the substrate without impairing the flexibility, and the peeling resistance and tear resistance of the headlining can be improved. It can be compatible in high dimensions.

As the polyolefin-based resin film, a multi-layer film obtained by combining polyethylene or polypropylene of different compositions with different glass transition temperatures can be suitably used for the purpose of increasing the strength of the base material without impairing the flexibility. It is possible to achieve both peeling resistance and tear resistance of the lining at a high level.

As the polyolefin resin film, a film having a thickness of 10 μm to 200 μm, preferably a film having a thickness of 15 μm to 100 μm, and a film having a thickness of 20 μm to 80 μm can be used as long as the strength of the substrate can be increased without impairing the flexibility. are more preferred, those of 30 μm to 60 μm are even more preferred, and those of 40 μm to 50 μm are particularly preferred.

Examples of the polyethylene film include LDPE (low density polyethylene), LLDPE (linear low density polyethylene or linear low density polyethylene), PE/EVA (polyethylene/vinyl acetate copolymer resin), HDPF (high density polyethylene), and the like. is mentioned.

Examples of LDPE films include those manufactured by Tamapoly Co., Ltd., including V series grades V-1, V-2, VE-7, etc., A series grade A-1, etc., and AJ series grade AJ-1. , M-series grade M-6, GF-series grades GF-1 and GF-3, and the like.

Examples of the LLDPE film include those manufactured by Tamapoly Co., Ltd., for example, UB series grades UB-1, UB-106, UB-105, UB-3, UB-1T, UB-106T, UB-0B, etc. , UH/UL series grades UH-1, UL-1, etc., NB series grades NB-1, etc., LC series grades LC-2 (T), LC-205 (T), etc., and series grades Although the range of thickness differs for each, the range of thickness is 30 μm to 150 μm. In addition, Toyobo Ricks Film (trade name) manufactured by Toyobo Co., Ltd. is exemplified. Although the lineup is different, there are 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 100 μm, and the like. Also, products manufactured by Futamura Chemical Co., Ltd. can be mentioned. Examples include XMTD, LL-XHT, LL-RP2, etc. The lineup of thicknesses differs for each product type, but examples include 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 100 μm, and 150 μm. Also, T.C. manufactured by Mitsui Chemicals Tohcello, Inc. U.S.A. X (trade name), and general grade items include HC, HC-E, FC-D, FCD-NP, FC-S, MC-S, TCS, TCS-NP, and VCS, Special grades include HZR-2, HZ, FCS-U, ECF-U, TNF, PRC, and PRUC. 70 μm, 80 μm, 100 μm, 120 μm, 130 μm, 150 μm, and the like. Another example is Elsmart manufactured by Mitsui Chemicals Tohcello (manufactured).

Examples of PE/EVA films include those manufactured by Tamapoly Co., Ltd., including AV series grade AV-51 and the like, and SB series grades SB-3, SB-5, and SB-7. Although the range of thickness is different for each grade, it may be 30 μm to 180 μm.

HDPE films include, for example, Caralyan Y (trade name) and Caralyan YA2 (trade name) manufactured by Denka Co., Ltd., and the standard thickness thereof is 18 μm.

As the polypropylene film, a film produced by cooling a molten high-temperature resin (so-called unstretched film) or a film produced by stretching (so-called uniaxially stretched film or biaxially stretched film) can be used.

Examples of the non-stretched polypropylene film include CPP films manufactured by FILMAX Co., Ltd. Examples of film types include CPG, CPS-1, CPM, CPT, etc. Although the thickness lineup differs for each film type, 20 μm, 25 μm, 30 μm, 40 μm, etc. can be mentioned. Also, Pylen Film-CT (trade name) manufactured by Toyobo Co., Ltd. is exemplified. Although the thickness lineup is different, there are 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm and the like.

Examples of the biaxially stretched polypropylene film (OPP film) include OPP films manufactured by Futamura Chemical Co., Ltd., and examples thereof include FOA, FOS, FOS-AQ, FOS-BT, etc., and the thickness of each product varies. Although the lineup differs, there are 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, and the like. Also, Pylen Film-OT (trade name) manufactured by Toyobo Co., Ltd. is exemplified. P5573, P5767, P3162, P6181, P8155, P4255, P4256, P6155, etc., and the lineup of thicknesses differs for each product name, but thicknesses of 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm, 60 μm, etc. mentioned. Examples include OPP films manufactured by Mitsui Chemicals Tocello Co., Ltd. General-purpose films (single-layer structure) include general-grade items such as OP U-0, OP U-1, and OP U-2. Non-antistatic grade items include OP M-1, OP M-2, OP ME-1, etc. Although the thickness lineup differs for each item, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, etc. Also, as multilayer heat seal films, single-sided heat-sealed items include HC-OP, and double-sided heat-sealed items include WH-OP OW-1 and WH-OP OW-1LS. , WH-OP F-1, etc., and the thickness lineup differs for each item, but 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, etc. are listed, and special films include anti-fog grade items. Examples include WH-OP NFHC, etc. Matte grade items include OP mat-1, WH-OP mat-1K, WH-OP FM-0, etc. High moisture-proof grade items include: WH-OP HM-1, WH-OP HE-1, etc. are mentioned, and although the thickness lineup differs for each item, 20 μm, 25 μm, 30 μm, etc. can be mentioned. In addition, an OPP film manufactured by FILMAX Co., Ltd. can be mentioned, and transparent film grades include BG, BG-R, BG-T, BT and the like. 30 μm, 40 μm, and the like. In addition, heat seal film grades include SG, SO, SL, SX, SG-S, etc. Although the thickness lineup differs for each grade, there are 18 μm, 20 μm, 25 μm, 30 μm, 40 μm, etc. mentioned.

Examples of the uniaxially stretched polypropylene film include those manufactured by Futamura Chemical Co., Ltd., and examples thereof include MCMD-AS, PP3K, and the like. etc.

Examples of multilayer films composited using polyolefins of different compositions include DIFAREN (trade name) manufactured by DIC Corporation. Brands of polypropylene multilayer films (PP/PP/PP) include B1155T and B2100T. , B1130TA, 180T, B2350T, P2160T, L2100T, etc., and thickness lineups differ for each brand, but thicknesses of 20 μm, 25 μm, 30 μm, 40 μm, etc. can be mentioned. Brands of composite multilayer films (PP/PE/PP or PP/PP/PE) of polypropylene and polyethylene include P2150T, 254N, etc., and thicknesses of 25 μm, 30 μm, 40 μm, 50 μm, and the like. Moreover, M212 etc. are mentioned as a composite multilayer film (PP/PE/EVA) of a polypropylene, a polyethylene, and a vinyl acetate copolymer, and a thing with a thickness of 25 micrometers etc. is mentioned. In addition, the brands of linear low-density polyethylene multilayer films (LLDPE/LLDPE/LLDPE) include L3501T, L3300T, etc., and although the thickness lineup differs for each brand, 40 μm, 50 μm, 60 μm, etc. can be mentioned. . In addition, the brands of multilayer films (PP/LLDPE/LLDPE) of polypropylene and linear low-density polyethylene include R3360T, E3311T, E3312T, E3701T, E3901T, E3801T, etc., and the thickness lineup differs for each brand. , 30 μm, 35 μm, 40 μm, 50 μm, and the like.

As the multilayer film, a multilayer film obtained by combining a polyester resin or a nylon resin may be used in addition to the polyolefin resin. Examples include DIFAREN (trade name) manufactured by DIC Corporation, and examples of brands of composite multilayer films (LLDPE/LLDPE/polyester) of linear low-density polyethylene and polyester resin include E7800PET, E7810PET, and E7800TT. , 25 .mu.m, 30 .mu.m, etc. are mentioned, although the lineup of the thickness differs for each brand.

(soft metal foil)
The soft metal foil is characterized by excellent shape retention. When a general film with poor shape retention is used as a base material, it is difficult to follow the shape of the cylindrically curved surface of the wire harness. easier. On the other hand, when the soft metal foil is used as a base material, or when a base material obtained by laminating the soft metal foil and the polyolefin resin film is used, the shape retention of the soft metal foil prevents the folded state. Since the stress of the wire harness is relaxed and the wire harness is not easily peeled off, it can be suitably used for fixing the wire harness to the headlining.

Examples of the soft metal foil include aluminum foil, magnesium foil, copper foil, tin foil, palladium foil, and brass foil (Western foil). Among them, aluminum foil, magnesium foil, and copper foil can be suitably used from the viewpoint of properties such as strength, and aluminum foil and magnesium foil are more preferable from the viewpoint of properties such as lightness and corrosion resistance in addition to strength. Aluminum foil can be used particularly preferably because it can be used favorably and can be easily processed for printing, embossing, and slitting. If necessary, other metal elements or non-metal elements such as carbon and boron may be added and melted together (so-called alloy foil).

Examples of the aluminum foil include those manufactured by UACJ Foil Co., Ltd., manufactured by Toyo Aluminum Co., Ltd., manufactured by Nippon Light Metal Co., Ltd., and the like.

The thickness of the soft metal foil can be 5 μm to 100 μm, preferably 12 μm to 100 μm, more preferably 30 μm to 100 μm, in order to achieve both tear resistance and peeling resistance. In addition, from the viewpoint of lightness while achieving both tear resistance and peeling resistance, those with a thickness of 30 μm to 80 μm are more preferably used, and those with a thickness of 50 μm to 80 μm are even more preferably used, 50 μm is particularly preferably used.

As a method for preparing a base material in which the soft metal foil and the polyolefin resin film are laminated, there are dry lamination by applying an adhesive, thermal lamination by heating the film to melt it by heating and bonding by pressure, and hot-melt resin. Examples include a resin fusion coating process in which a metal foil is directly coated and bonded while being melted. Among them, dry lamination is preferable because a lamination structure can be easily prepared regardless of the thickness of the soft metal foil and the polyolefin resin film.

When laminating the soft metal foil and the polyolefin-based resin film by dry lamination, the polyolefin-based resin film is preliminarily subjected to easy-contact treatment, or is subjected to easy-contact treatment such as corona discharge treatment. It is preferably used after application.

Examples of the adhesive used for dry lamination include polyester adhesives, polyether adhesives, polyurethane adhesives, and the like. agents can be preferably used. Polyurethane-based adhesives can be used more preferably when used in applications that require high resistance in addition to the above properties.

Combinations of the polyester adhesive/curing agent used in the dry lamination include, for example, Dick Dry LX-500/KW-75, Dick Dry LX-520/KO40, and Dick Dry LX-703VL manufactured by DIC Graphics Co., Ltd. /KR-90, Dick Dry LX-732/KVM-90, Dick Dry LX-906/KO55, Dick Dry LX-963/KO-40, Dick Dry LX-901/KW-75, etc., manufactured by Toyo Ink Co., Ltd. TM-250HV/CAT-RT86, TM-595/CAT-56, TM-265L/CAT-RT37, AD-502/CAT-10, AD-556/CAT-56, AD-811/CAT-RT8, AD -817/CAT-RT56, AD-900/CAT-RT85, etc., Takelac A-310/Takenate A-3, Takelac A-315/Takenate A-10, Takelac A-385/Takenate A manufactured by Mitsui Chemicals, Inc. -50, Takelac A-515/Takenate A-50, Takelac A-520/Takenate A-50, Takelac A-525/Takenate A-52, Takerac A-606/Takenate A-10, Takelac A-620/Takenate A -65, Takelac A-626 / Takenate A-50, Takelac A-627 / Takenate A-65, Takelac A-975 / Takenate A-3, etc., Dainichiseika Kogyo Co., Ltd. Seikabond E-366 / C- 83, E-370/C-84, E-372/C-76, A601/C84 and the like. Further, as a combination of polyether adhesive/curing agent, for example, Dick Dry LX-401A/SP-60, Dick Dry LE-3100/SL-75 manufactured by DIC Graphics Co., Ltd., Dainichiseika Kogyo Co., Ltd. Seikabond A-159/C-89F manufactured by Co., Ltd. and the like can be mentioned. Examples of polyurethane-based adhesives include one-component moisture-curing polyurethane resins (trade name: Yunoflex series) and two-component-curing polyurethane resins (trade name: Polybond series) manufactured by Sanyo Chemical Industries, Ltd.

Adhesives used for dry lamination are organic solvents such as ethyl acetate, butyl acetate, cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, toluene, xylene, methylene chloride, ethylene chloride, dimethylsulfoxide, and dimethylsulfamide. , but ethyl acetate and methyl ethyl ketone are preferably used from the viewpoint of solubility and environmental load reduction.

The method of applying the adhesive used in dry lamination includes gravure roll coating, direct roll coating, and reverse roll coating, and the method of application is appropriately selected according to the required coating amount. The base material to which the adhesive is applied may be a polyolefin resin film or a soft metal foil.

After removing the diluting solvent from the adhesive applied by the above-described method in a drying process, the soft metal foil and the polyolefin resin film are bonded together and pressure-bonded using a heat lamination roll. For the purpose of efficiently removing the diluent solvent, the drying temperature can be appropriately adjusted, but it is preferably adjusted within the range of 60° C. to 110° C. in order to prevent expansion or shrinkage of the base material used. Similarly, the drying time can be appropriately adjusted, but it is preferable to adjust the drying time within the range of 10 seconds to 3 minutes for the reason of preventing expansion or shrinkage of the substrate used.

It is preferable that the base material obtained by laminating the soft metal foil and the polyolefin resin film prepared by the above method is cured in an atmosphere of 30° C. to 60° C. for 2 to 5 days in order to accelerate the curing reaction of the adhesive.

The substrate obtained by laminating the soft metal foil and the polyolefin resin film preferably has a thickness of 27 μm to 200 μm, more preferably 50 μm to 180 μm, in order to achieve both tear resistance and peeling resistance. is more preferably 60 μm to 160 μm thick, even more preferably 80 μm to 140 μm thick, and most preferably 90 μm to 100 μm thick.

The substrate obtained by laminating the soft metal foil and the polyolefin resin film has a ratio of thicknesses of the polyolefin resin film and the soft metal foil (the thickness of the polyolefin resin film /thickness of the soft metal foil) is preferably in the range of 0.05 to 10, more preferably in the range of 0.1 to 5, and preferably in the range of 0.15 to 3.5. Even more preferably in the range of 0.2 to 1.5, even more preferably in the range of 0.3 to 1.2, even more preferably in the range of 0.4 to 0.9 is particularly preferred.

<Adhesive layer>
The pressure-sensitive adhesive layer preferably has a thickness of 25 μm to 70 μm in order to achieve both excellent adhesive strength and peeling resistance when used exclusively to fix the wire harness to the headlining. , more preferably 30 μm to 65 μm, particularly preferably 40 μm to 60 μm.

The pressure-sensitive adhesive layer provided on the laminated substrate is formed using a pressure-sensitive adhesive composition containing a styrene-isoprene block copolymer and a hydrocarbon resin.

(styrene-isoprene block copolymer)
The styrene-isoprene block copolymer may have a linear structure, a radial structure, or a branched structure, and can be appropriately selected and used according to the usage and environmental conditions. When used for fixing, those having a linear structure can be preferably used in order to achieve both excellent adhesive strength and peeling resistance.

The styrene-isoprene block copolymer preferably has a styrene content in the range of 10% by mass to 50% by mass, more preferably 14% by mass to 25% by mass, in order to achieve both excellent adhesive strength and peeling resistance. %, and even more preferably 15% to 20% by mass.

The styrene-isoprene block copolymer is of a styrene-isoprene (SI) diblock structure or of a styrene-isoprene-styrene (SIS) triblock structure, or of a SI diblock structure and a SIS triblock structure. It is preferable to use a mixture, preferably one substantially free of styrene homopolymer, isoprene homopolymer, and styrene-isoprene random copolymer structures.

In the styrene-isoprene block copolymer, the diblock content is preferably in the range of 10% by mass to 80% by mass, and 30% by mass to It is more preferably in the range of 80 mass %, even more preferably in the range of 50 mass % to 80 mass %, and particularly preferably in the range of 55 mass % to 80 mass %.

The diblock content means the amount (ratio/ratio) of the SI diblock structure to the total amount of the SI diblock structure and the SIS triblock structure.

The diblock content can be calculated from the ratio of the peak area of the SI diblock structure to the peak area of the SIS triblock structure obtained from the elution curve using gel permeation chromatography (GPC).

The styrene-isoprene block copolymer may be in the form of pellets (granules with high bulk density), crumbs (porous granules), powder, or liquid. Although they can be appropriately selected and used together, pellets or crumbs are preferably used, and pellets are more preferably used, from the viewpoint of ease of handling in the production of the pressure-sensitive adhesive composition.

Specific examples of the styrene-isoprene block copolymer include the Quintac series manufactured by Nippon Zeon Co., Ltd. The grade is 3620 (polymer structure: linear/radial mixture, styrene content: 14% by mass, SI diblock content: 12% by mass), 3421 (polymer structure: linear, styrene content: 14% by mass, SI diblock content: 26% by mass), 3433N (polymer structure: linear, styrene content: 16% by weight, SI diblock content: 56% by weight), 3520 (polymer structure: linear, styrene content: 15% by weight, SI diblock content: 78% by weight), 3450 (polymer structure: radial, styrene content: 19% by mass, SI diblock content: 30% by mass), 3280 (polymer structure: linear, styrene content: 25% by mass, SI diblock content: 17% by mass), 3270 (polymer structure: linear, styrene content: 24% by mass, SI diblock content: 67% by mass) and the like. In addition, SIS5229 (styrene content: 15% by mass, SI diblock content: 20% by mass), SIS5002 (styrene content: 22% by mass, SI diblock content: 15% by mass) manufactured by JSR Corporation, SIS5403P (styrene content: 15% by mass, SI diblock content: 40% by mass), SIS5506P (styrene content: 16% by mass, SI diblock content: 55% by mass), SIS5250P (styrene content: 20% by mass %, SI diblock content: 30% by mass) and the like. In addition, the Kraton D polymer series manufactured by Kraton Polymer Co. (USA) can be mentioned, and the grades include D1111 (polymer structure: linear, styrene content: 22% by mass, SI diblock content: 18% by mass), DX401. (polymer structure: linear, styrene content: 22% by mass, SI diblock content: 18% by mass), D1113 (polymer structure: linear, styrene content: 16% by mass, SI diblock content: 55% by mass) %), D1114 (polymer structure: linear, styrene content: 19% by mass, SI diblock content: 1% by mass), D1160 (polymer structure: linear, styrene content: 19% by mass, SI diblock content amount: 1% by mass), D1117 (polymer structure: linear, styrene content: 17% by mass, SI diblock content: 33% by mass), D1119 (polymer structure: linear, styrene content: 22% by mass, SI diblock content: 66% by mass), D1124 (polymer structure: radial, styrene content: 30% by mass, SI diblock content: 29% by mass), D1126 (polymer structure: radial, styrene content: 21% by mass %, SI diblock content: 30% by mass), D1161 (polymer structure: linear, styrene content: 15% by mass, SI diblock content: 19% by mass), D1162 (polymer structure: linear, styrene-containing amount: 43% by weight, SI diblock content: 1% by weight), D1163 (polymer structure: linear, styrene content: 15% by weight, SI diblock content: 38% by weight), D1164 (polymer structure: linear styrene content: 29% by mass, SI diblock content: 1% by mass), and the like.

(hydrocarbon resin)
As the hydrocarbon resin, for example, an aliphatic hydrocarbon resin using 1,3-pentadiene extracted from the C5 fraction obtained by cracking naphtha as the main raw material, or dicyclopentadiene extracted from the C5 fraction is used as the main raw material. Aromatic hydrocarbon resin using styrene, vinyltoluene, indene, etc. extracted from the C9 fraction as the main raw material, styrene, vinyltoluene, indene, etc. extracted from the C5 and C9 fractions. Examples include aliphatic/aromatic copolymer hydrocarbon resins using piperylene etc. as the main raw material. /Aromatic copolymer-based hydrocarbon resins can be preferably used, and among them, aliphatic/aromatic copolymer-based hydrocarbon resins can be used more preferably.

The hydrocarbon resin preferably has a softening point in the range of 80° C. to 150° C., more preferably in the range of 90° C. to 140° C., in order to achieve both excellent adhesive strength and peeling resistance. It is more preferably in the range of 95°C to 130°C, and particularly preferably in the range of 100°C to 120°C.

The softening point of the hydrocarbon resin can be calculated by measuring according to JIS K 2207 ring and ball formula.

Specific examples of the hydrocarbon resin include Quintone 100 series manufactured by Nippon Zeon Co., Ltd. Grades include A100 (aliphatic hydrocarbon resin, softening point: 100 ° C.), B170 (aliphatic Hydrocarbon resin, softening point: 70°C), R100 (aliphatic hydrocarbon resin, softening point: 96°C), S195 (aliphatic/aromatic copolymer hydrocarbon resin, softening point: 94°C), D100 ( Aliphatic/aromatic copolymerized hydrocarbon resin, softening point: 99°C), U185 (aliphatic/aromatic copolymerized hydrocarbon resin, softening point: 86°C), DX395 (aliphatic/aromatic copolymerized hydrocarbon resin, softening point: 94°C), DX390N (aliphatic/aromatic copolymerized hydrocarbon resin, softening point: 93°C), N180 (aliphatic/aromatic copolymerized hydrocarbon resin, softening point: 80 ° C.), G100B (aliphatic/aromatic copolymer hydrocarbon resin, softening point: 100 ° C.), G115 (aliphatic/aromatic copolymer hydrocarbon resin, softening point: 115 ° C.), CX495 (aliphatic hydrocarbon resin, softening point: 96°C), C210 (aliphatic hydrocarbon resin, softening point: 110°C), E200SN (aliphatic/aromatic copolymer hydrocarbon resin, softening point: 102°C), D200 ( aliphatic/aromatic copolymer hydrocarbon resin, softening point: 102° C.) and the like. Further, the Quintone 1000 series manufactured by Nippon Zeon Co., Ltd. can be mentioned, and the grades include 1105 (alicyclic hydrocarbon resin, softening point: 107°C), 1325 (alicyclic hydrocarbon resin, softening point: 125 ° C.), TD-401 (alicyclic hydrocarbon resin, softening point: 140 ° C.), 1500 (alicyclic hydrocarbon resin, softening point: 100 ° C.), 1525L (alicyclic hydrocarbon resin, softening point: 125°C), 1920 (alicyclic hydrocarbon resin, softening point: 120°C), 2940 (alicyclic hydrocarbon resin, softening point: 140°C), and the like. Also, Maruzen Petrochemical Co., Ltd. Marukaretsu M series, grades include M-890A (alicyclic hydrocarbon resin, softening point: 105 ° C.), M-845A (alicyclic hydrocarbon resin, softening point: 145° C.) and the like. Also, Petcol manufactured by Tosoh Corporation can be mentioned, and grades include LX (aromatic hydrocarbon resin, softening point: 98°C), 120 (aromatic hydrocarbon resin, softening point: 120), 130 ( aromatic hydrocarbon resin, softening point: 125°C), 140 (aromatic hydrocarbon resin, softening point: 135°C), and the like. Also, Petrotac manufactured by Tosoh Corporation can be mentioned, and grades include 60 (aromatic hydrocarbon resin, softening point: 72°C), 70 (aromatic hydrocarbon resin, softening point: 70°C), 90 (aromatic hydrocarbon resin, softening point: 95°C), 90V (aromatic hydrocarbon resin, softening point: 87°C), 100V (aromatic hydrocarbon resin, softening point: 96°C), 120V ( aromatic hydrocarbon resin, softening point: 120°C), 130V (aromatic hydrocarbon resin, softening point: 130°C), and the like. In addition, NOVARES manufactured by Novares Rutgers (Germany) can be mentioned. : 115°C to 125°C), TT140 (aromatic hydrocarbon resin, softening point: 135°C to 140°C), TL90 (aromatic hydrocarbon resin, softening point: 85°C to 95°C), TL100 (aromatic hydrocarbon resin, softening point: 95° C. to 105° C.), TL120 (aromatic hydrocarbon resin, softening point: 115° C. to 125° C.). Eastotac series manufactured by Eastman Chemical Co. (USA) can also be mentioned, and examples of grades include C-100L Resin (aliphatic hydrocarbon resin, softening point: 100° C.). Also, the Piccotac series manufactured by Eastman Chemical Company (USA) can be mentioned, and the grades include 1100 Hydrocarbon Resin (aliphatic hydrocarbon resin, softening point: 100 ° C.), 1100-E Hydrocarbon Resin (aliphatic hydrocarbon resin, softening point: 99° C.) and the like. In addition, the FTR series manufactured by Mitsui Chemicals, Inc. can be mentioned, and the grades include FTR0100 (aromatic hydrocarbon resin, softening point: 100°C) and FTR2120 (aromatic hydrocarbon resin, softening point: 125°C). , FTR2140 (aromatic hydrocarbon resin, softening point: 137° C.). In addition, the T-REZ R series manufactured by Standard Oil Osaka Co., Ltd. can be mentioned, and the grades include T-REZ RA100 (aliphatic hydrocarbon resin, softening point: 95 ° C. to 105 ° C.), T-REZ RB100 (aliphatic hydrocarbon resin, softening point: 95°C to 105°C), T-REZ RC093 (aliphatic hydrocarbon resin, softening point: 88°C to 98°C), T-REZ RC100 (aliphatic carbonized hydrogen resin, softening point: 95°C to 105°C), T-REZ RC115 (aliphatic hydrocarbon resin, softening point: 110°C to 120°C), T-REZ RD104 (aliphatic/aromatic copolymer hydrocarbon resin, softening point: 99° C. to 109° C.) and the like. In addition, Alcon P-90 (alicyclic saturated hydrocarbon resin, softening point: 90 ° C.), Alcon P-100 (alicyclic saturated hydrocarbon resin, softening point: 100 ° C.) manufactured by Arakawa Chemical Industries, Ltd., Alcon P-115 (alicyclic saturated hydrocarbon resin, softening point: 115 ° C.), Alcon P-125 (alicyclic saturated hydrocarbon resin, softening point: 125 ° C.), Alcon P-140 (alicyclic saturated carbon Hydrogen resin, softening point: 140°C), Alcon M-90 (alicyclic saturated hydrocarbon resin, softening point: 90°C), Alcon M-100 (alicyclic saturated hydrocarbon resin, softening point: 100°C), Alcon M-115 (alicyclic saturated hydrocarbon resin, softening point: 115°C), Alcon M-135 (alicyclic saturated hydrocarbon resin, softening point: 135°C), and the like.

The mass ratio of the content of the styrene-isoprene block copolymer to the content of the hydrocarbon resin (styrene-isoprene block copolymer/hydrocarbon resin) is preferably in the range of 0.5 to 20, preferably 1 to 10. more preferably in the range of 1.5 to 5, even more preferably in the range of 2.5 to 4, and even more preferably in the range of 2.6 to 3.5 is particularly preferred.

(tackifying resin)
The pressure-sensitive adhesive layer can use tackifying resins such as rosin-based resins, terpene-based resins, styrene-based resins, coumarone resins, and xylene resins, in addition to styrene-isoprene block copolymers and hydrocarbon resins. Among them, rosin-based resins and terpene-based resins are preferably used, and rosin-based resins are more preferably used, in order to achieve both excellent adhesive strength and peeling resistance. A resin selected from the group consisting of rosin-based resins, terpene-based resins, styrene-based resins, coumarone resins, and xylene resins may be used, or two or more thereof may be used in combination.

The amount (total amount) of the tackifying resin used is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and 15 parts by mass to 45 parts by mass with respect to 100 parts by mass of the styrene-isoprene block copolymer. Parts by weight are even more preferred, 20 to 40 parts by weight are even more preferred, and 25 to 35 parts by weight are particularly preferred.

The softening point of the tackifying resin is preferably in the range of 100°C to 180°C, more preferably in the range of 120°C to 175°C, and more preferably in the range of 130°C to 170°C. It is particularly preferred to use

Examples of the rosin-based resin include rosin ester, stabilized rosin ester, special rosin ester, disproportionated rosin, polymerized rosin, polymerized rosin ester, rosin-modified phenolic resin, modified rosin pentaerythritol ester, rosin-modified glycerin ester, and rosin-modified malein. Examples include acid resins, rosin derivatives, hydrogenated rosins, ultra-light colored rosins, and ultra-light colored rosin esters. Among them, a special rosin ester and a polymerized rosin ester are more preferably used, and a polymerized rosin ester is particularly preferably used, in order to achieve both excellent adhesive strength and peeling resistance.

Examples of the terpene-based resins include terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated terpene phenol resins, hydrogenated terpene resins, and hydrogenated aromatic modified terpene resins. Among them, a terpene phenol resin can be used more preferably in terms of achieving both excellent adhesive strength and peeling resistance.

Specific examples of the rosin-based resin include Aladim R-95 (polymerized rosin, softening point: 93° C. to 103° C.) manufactured by Arakawa Chemical Industries, Ltd., ester gum AA-L (rosin ester, softening point: 93° C. to 103° C.), 82°C), Estergum 105 (rosin ester, softening point: 100°C to 110°C), Estergum H (hydrogenated rosin ester, softening point: 68°C), Estergum HP (hydrogenated rosin ester, softening point: 80°C) ° C.), Pencel GA-100 (rosin ester, softening point: 100° C.), Pencel AZ (rosin ester, softening point: 95° C. to 105° C.), Pencel D-125 (polymerized rosin ester, softening point: 120° C. to 130° C.) ° C.), Pencel D-135 (polymerized rosin ester, softening point: 130°C to 140°C), Pencel D-160 (polymerized rosin ester, softening point: 150°C to 165°C), Super Ester A-75 (special rosin ester , softening point: 70°C to 80°C), Super Ester A-100 (special rosin ester, softening point: 95°C to 105°C), Super Ester A-115 (special rosin ester, softening point: 108°C to 120°C) , Super Ester A-125 (special rosin ester, softening point: 120°C to 130°C), Tamanol 135 (rosin-modified phenol, softening point: 130°C to 140°C), Pine Crystal KR-85 (ultra-light colored rosin, softening point : 80°C to 87°C), Pine Crystal KR-612 (Ultra pale rosin, softening point: 80°C to 90°C), Pine Crystal KR-614 (Ultra pale rosin, softening point: 84°C to 94°C), Pine Crystal KE-100 (ultra-light color rosin ester, softening point: 95°C-105°C), Pine Crystal KE-311 (ultra-light color rosin ester, softening point: 90°C-100°C), Pine Crystal KE-359 (ultra-light color rosin ester) , softening point: 94° C. to 104° C.), Hypal CH (hydrogenated rosin, softening point: 65° C.), and the like. Harima Kasei Co., Ltd. Harrier Star TF (rosin-modified glycerin ester, softening point: 75° C. to 85° C.), Harrier Star S (rosin-modified glycerin ester, softening point: 68° C. to 73° C.), Neotol G2 ( Stabilized rosin half ester, softening point: 97°C to 104°C),
Neotol 101N (stabilized rosin ester, softening point: 93°C to 103°C), Neotol 125HK (modified rosin pentaerythritol ester, softening point: 120°C to 130°C), Haritak 8LJA (rosin ester, softening point: 82°C to 92°C) ° C.), HARITAC ER95 (rosin ester, softening point: 85° C. to 98° C.), HARITAC SE10 (stabilized rosin ester, softening point: 78° C. to 87° C.), HARITAC PH (stabilized rosin ester, softening point: 93° C.) ~101°C), HARITAC F85 (stabilized rosin ester, softening point: 80°C to 90°C), HARITAC F105 (stabilized rosin ester, softening point: 97°C to 107°C), HARITAC FK100 (stabilized rosin ester, softening point: 96°C to 102°C), HARITAC FK125 (stabilized rosin ester, softening point: 122°C to 128°C), HARITAC PCJ (polymerized rosin ester, softening point: 118°C to 128°C), HARIMAC T-80 (rosin modified maleic acid resin, softening point: 80° C. to 90° C.), HARIMAC R-100 (rosin modified maleic acid resin, softening point: 100° C. to 110° C.), HARIMAC M-453 (rosin modified maleic acid resin, softening point: 100°C to 110°C), HARITAC 4851 (rosin-modified maleic acid resin, softening point: 95°C to 105°C), HARITAC 4821 (rosin-modified maleic acid resin, softening point: 100°C to 115°C), HARITAC 4740 (rosin-modified maleic acid resin, softening point: 115° C. to 125° C.), HARITAC 28JA (rosin-modified maleic acid resin, softening point: 130° C. to 140° C.), and the like. In addition, Sylvalite RE80HP (rosin ester, softening point: 80°C), Sylvalite RE85L (rosin ester, softening point: 85°C), Sylvalite RE100L (rosin ester, softening point: 100°C), Sylvalite manufactured by Kraton Polymer Co. (USA) RE105L (rosin ester, softening point: 105°C), Sylvalite RE85LK (rosin ester, softening point: 85°C), Sylvalite RE100XL (rosin ester, softening point: 98°C), Sylvalite RE115 (rosin ester, softening point: 115°C) , Sylvatac RE85 (rosin ester, softening point: 83 ° C.), Sylvatac RE98 (rosin ester, softening point: 93 ° C.), Sylvatac RE94 (rosin ester, softening point: 96 ° C.), Sylvatac RE100 (rosin ester, softening point: 100 ° C.), Sylvatac RE100NS (rosin ester, softening point: 100° C.), and the like.

Specific examples of the terpene resin include YS Polystar U130 (terpene phenol resin, softening point: 130°C), YS Polystar U115 (terpene phenol resin, softening point: 115°C) and YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd. (terpene phenol resin, softening point: 160° C.), YS Polystar T145 (terpene phenol resin, softening point: 145° C.), YS Polystar T130 (terpene phenol resin, softening point: 130° C.), YS Polystar T115 (terpene phenol resin, softening point: 130° C.) softening point: 115°C),
YS Polystar T100 (terpene phenol resin, softening point: 100° C.), YS Polystar T80 (terpene phenol resin, softening point: 80° C.), YS Polystar S145 (terpene phenol resin, softening point: 145° C.), YS Polystar G150 (terpene Phenolic resin, softening point: 150 ° C.), YS Polystar G125 (terpene phenol resin, softening point: 125 ° C.), YS Polystar N125 (terpene phenol resin, softening point: 125 ° C.), YS Polyster K125 (terpene phenol resin, softening point : 125°C), YS Polystar TH130 (terpene phenol resin, softening point: 130°C), YS Resin PX1250 (terpene resin, softening point: 125°C), YS Resin PX1150 (terpene resin, softening point: 115°C), YS resin PX1000 (terpene resin, softening point: 100°C), YS Resin PX800 (terpene resin, softening point: 80°C), YS Resin PX1150N (terpene resin, softening point: 115°C), YS Resin TO125 (aromatic modified terpene resin, softening point: 125°C), YS Resin TO115 (aromatically modified terpene resin, softening point: 115°C), YS Resin TO105 (aromatically modified terpene resin, softening point: 105°C), YS Resin TO85 (aromatically modified terpene resin , softening point: 85°C), YS Polystar UH115 (hydrogenated terpene phenolic resin, softening point: 115°C), and the like. Further, Tamanol 803L (terpene phenol, softening point: 145° C. to 160° C.) and Tamanol 901 (terpene phenol, softening point: 125° C. to 135° C.) manufactured by Arakawa Chemical Industries, Ltd. may be used. In addition, Sylvares TRB115 (polyterpene resin, softening point: 116 ° C.), Sylvares TR1115T (polyterpene resin, softening point: 116 ° C.), Sylvares TR7115 (polyterpene resin, softening point: 115 ° C.), Sylvares manufactured by Kraton Polymer Co. (USA) TRM1115 (polyterpene resin, softening point: 115°C), Sylvares TR7125 (polyterpene resin, softening point: 125°C), Sylvares TRB125 (polyterpene resin, softening point: 125°C), Sylvares TR1135 (polyterpene resin, softening point: 135°C) , Sylvares TR1135 (polyterpene resin, softening point: 135 ° C.), Sylvares TR90 (polyterpene resin, softening point: 90 ° C.), Sylvares TR105 (polyterpene resin, softening point: 105 ° C.), Sylvares TP95 (terpene phenolic resin, softening point: 95 ° C.), Sylvares TP96 (terpene phenol resin, softening point: 95 ° C.), Sylvares TP300 (terpene phenol resin, softening point: 112 ° C.), Sylvares TP2040 (terpene phenol resin, softening point: 118 ° C.), Sylvares TP2019 (terpene Phenolic resin, softening point: 125°C), Sylvares TP2040HM (terpene phenolic resin, softening point: 125°C), Sylvares TP7042 (terpene phenolic resin, softening point: 145°C), Sylvares TP105 (terpene phenolic resin, softening point: 105°C) ), Sylvares TP115 (terpene phenol resin, softening point: 115°C), Sylvares ZT105LT (styrene-modified terpene resin, softening point: 105°C), Zonatac NG98 (styrene-modified terpene resin, softening point: 98°C), and the like.

Specific examples of the styrene-based resin include YS Resin SX100 (styrene resin, softening point: 100° C.) manufactured by Yasuhara Chemical Co., Ltd., and the like.

The coumarone resin is a copolymer resin mainly composed of coumarone, indene, styrene and the like. 90° C.), knit resin cumarone V-120 (coumarone resin, softening point: 120° C.), and knit resin cumarone V-120S (coumarone resin, softening point: 120° C.).

Specific examples of the xylene resin include Nikanol Y-50 (xylene resin, softening point: liquid), Nikanol L (xylene resin, softening point: liquid), and Nikanol H (xylene resin, softening point) manufactured by Fudo Co., Ltd. point: liquid), Nikanol G (xylene resin, softening point: liquid), Nikanol GHP-150 (alkylphenol modified type xylene resin, softening point: 150°C to 160°C), Nikanol HP-120 (alkylphenol modified type xylene resin, softening point: 125°C to 135°C), Nikanol HP-100 (alkylphenol modified type xylene resin, softening point: 105°C to 125°C), Nikanol HP-210 (alkylphenol modified type xylene resin, softening point: 90°C to 110°C) , Nikanol HP-70 (alkylphenol modified type xylene resin, softening point: 70°C to 90°C), and the like. Also, Lignol R-70 (rosin-modified xylene resin, softening point: 75° C. to 85° C.) and Lignol R-140 (rosin-modified xylene resin, softening point: 128° C. to 135° C.) manufactured by Lignite Co., Ltd. be done.

(Other resins)
In addition to styrene-isoprene block copolymers and hydrocarbon resins, the adhesive layer includes paraffinic oils, naphthenic process oils, aromatic process oils, other process oils, liquid polyisoprene, liquid polybutadiene, and liquid styrene-butadiene. Rubber, liquid polybutene, and other liquid rubbers can be preferably used. Liquid polyolefin obtained by hydrogenating liquid polyisoprene (liquid hydrogenated polyisoprene), liquid polybutadiene modified with maleic acid (maleic acid-modified polybutadiene), liquid polybutadiene modified with epoxy (epoxy-modified polybutadiene), liquid polybutadiene Hydroxyl terminal modified polybutadiene, hydrogenated liquid polybutadiene (hydrogenated polybutadiene), terminal hydroxyl modified and hydrogenated liquid polybutadiene (hydroxyl terminal modified hydrogenated polybutadiene), terminal of liquid polybutadiene Polybutadiene with an acrylic group introduced into the terminal (polybutadiene with an acrylic group introduced at the end), liquid polybutadiene with an isocyanate group introduced at the terminal with an isocyanate group (polybutadiene with an isocyanate group introduced at the terminal), liquid polybutadiene with a hydroxyl group and a carboxyl group introduced at the terminal (hydroxyl group, Carboxyl group-introduced polybutadiene) and the like can also be preferably used. Among them, liquid polyisoprene, liquid polybutadiene, liquid styrene-butadiene rubber, and liquid polybutene are more preferable, and liquid polybutene is particularly preferable, in order to achieve both excellent adhesive strength and peeling resistance. Paraffinic oils, naphthenic process oils, aromatic process oils, other process oils, liquid polyisoprene, liquid polybutadiene, liquid styrene-butadiene rubber, liquid polybutene, other liquid rubbers, liquid hydrogenated polyisoprene, maleic acid-modified Using one type of resin selected from the group consisting of polybutadiene, epoxy-modified polybutadiene, terminal hydroxyl group-modified polybutadiene, hydrogenated polybutadiene, terminal hydroxyl group-modified hydrogenated polybutadiene, terminal acrylic group-introduced polybutadiene, terminal isocyanate group-introduced polybutadiene, and hydroxyl group/carboxyl group-introduced polybutadiene may be used, or two or more may be used in combination.

In addition to said styrene-isoprene block copolymers and hydrocarbon resins, said paraffinic oils, naphthenic processing oils, aromatic processing oils, other processing oils, liquid polyisoprene, liquid polybutadiene, liquid styrene-butadiene rubber, liquid polybutene. , Other liquid rubber, liquid hydrogenated polyisoprene, maleic acid-modified polybutadiene, epoxy-modified polybutadiene, terminal hydroxyl group-modified polybutadiene, hydrogenated polybutadiene, terminal hydroxyl group-modified hydrogenated polybutadiene, terminal acrylic group-introduced polybutadiene, terminal isocyanate group-introduced polybutadiene, hydroxyl group- When using carboxyl group-introduced polybutadiene, etc., the paraffinic oil, naphthenic process oil, aromatic process oil, other process oils, liquid polyisoprene, liquid polybutadiene, liquid styrene-butadiene rubber, liquid polybutene, etc. Liquid rubber, liquid hydrogenated polyisoprene, maleic acid-modified polybutadiene, epoxy-modified polybutadiene, terminal hydroxyl group-modified polybutadiene, hydrogenated polybutadiene, terminal hydroxyl group-modified hydrogenated polybutadiene, terminal acrylic group-introduced polybutadiene, terminal isocyanate group-introduced polybutadiene, hydroxyl group/carboxyl group The amount of the introduced polybutadiene or the like used is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of the styrene-isoprene block copolymer. parts are more preferred, and 5 to 10 parts by mass are particularly preferred.

Specific examples of the paraffin-based process oil include Diana Process Oil PW-2 and Diana Process Oil PW-90 manufactured by Idemitsu Kosan Co., Ltd. Further, SUNPAR 107, SUNPAR 110, SUNPAR 115, SUNPAR 150, SUNPAR 2100, SUNPAR 2280, SUNPURE LW70, SUNPURE LW500, SUNPURE P32, SUNPURE P22, SUNPURE P, etc. manufactured by Nippon Sun Oil Co., Ltd. may be mentioned. Process oil P100(K), process oil P200(K), process oil P300(K), process oil P400(K), process oil P500S, etc. manufactured by JXTG Energy Co., Ltd. can also be used. Also, barrel process oil P-6, barrel process oil P-18, barrel process oil P-26, barrel process oil P-46, barrel process oil P-56, barrel process oil P-150 manufactured by Matsumura Oil Co., Ltd. , barrel process oil P-380, barrel process oil P-1500 and the like.

Specific examples of the naphthenic process oil include Diana process oil NP-24 (a mixture of solvent-refined high-viscosity naphthene and solvent-refined low-viscosity naphthene) manufactured by Idemitsu Kosan Co., Ltd., Diana process oil NR-26 (mainly component: solvent-refined high-viscosity naphthene), Diana Process Oil NR-68 (main component: solvent-refined high-viscosity naphthene), Diana Process Oil NM-280 (main component: solvent-refined high-viscosity naphthene), and the like. SUNTHENE 410, SUNTHENE 415, SUNTHENE 450, SUNTHENE 4130, SUNTHENE 4240, SUNTHENE 250J, SUNPURE N90, SUNPURE NX90, etc. manufactured by Nippon Sun Oil Co., Ltd. may also be mentioned. Moreover, JXTG Energy Co., Ltd. Chrysef Oil H22, Chrysef Oil H68, Chrysef Oil H100, etc. are mentioned.

Specific examples of the aromatic process oil include Diana Process Oil AC-12 and Diana Process Oil AC-460 manufactured by Idemitsu Kosan Co., Ltd. In addition, JSO AROMA 790 manufactured by Nippon Sun Oil Co., Ltd. and the like can be used. Aromax 1, Aromax 3, Aromax EPX-1 and the like manufactured by Fuji Kosan Co., Ltd. may also be mentioned. Also, barrel process oil B-01, barrel process oil B-03, barrel process oil B-04AB, barrel process oil B-05, barrel process oil B-28AN, barrel process oil B-30 manufactured by Matsumura Oil Co., Ltd. etc.

Specific examples of the other process oils include Diana process oil NP-250 (mixture of solvent-refined high-viscosity naphthene and hydrogenated medium-viscosity paraffin), Diana process oil NS-90S (solvent-refined high-viscosity naphthene and hydrogenated mixture of viscous paraffins), Diana Process Oil NS-100 (mixture of solvent-refined high-viscosity naphthene and hydrogenated medium-viscosity paraffin), and the like. In addition, kyumic process oil L-NC and kyumic process oil 8465 manufactured by Shinnihon Yushi Kogyo Co., Ltd. may also be used.

Specific examples of the liquid polyisoprene include Claprene KL-10, Claprene LIR-30, Claprene LIR-50, Claprene LIR-310, Claprene LIR-390, Claprene LIR-403, and Claprene LIR manufactured by Kuraray Co., Ltd. -410, Claprene LIR-290, Claprene LIR-700 and the like. Further, Poly ip manufactured by Idemitsu Kosan Co., Ltd., and the like are included. Liquid polyolefins obtained by hydrogenating liquid polyisoprene include Epol manufactured by Idemitsu Kosan Co., Ltd., and the like.

Specific examples of the liquid polybutadiene include Claprene LBR-300, Claprene LBR-302, Claprene LBR-305, Claprene LBR-307, Claprene LBR-352, and Claprene LBR-361 manufactured by Kuraray Co., Ltd. . Also, Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157 manufactured by Clay Valley (USA), and the like. Poly bd R-15HT and Poly bd R-45HT manufactured by Idemitsu Kosan (manufactured by Idemitsu Kosan) are also included. Examples of the liquid polybutadiene modified with maleic acid (maleic acid-modified polybutadiene) include Ricon 130MA8, Ricon 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon 184MA6 manufactured by Clay Valley (USA). mentioned. Examples of the epoxy-modified liquid polybutadiene (epoxy-modified polybutadiene) include Ricon 657 manufactured by Clay Valley (USA), JP-100 manufactured by Nippon Soda Co., Ltd., and the like. Examples of the liquid polybutadiene obtained by modifying the terminal with a hydroxyl group (terminal hydroxyl group-modified polybutadiene) include Krasol LBH2000, Krasol LBH-P2000, Krasol LBH3000, Krasol LBH-P3000, Krasol HLBH-P2000, Krasol LBH-P2000, Krasol LBH-P2000, Examples include Krasol HLBH-P3000 and G-1000, G-2000 and G-3000 manufactured by Nippon Soda Co., Ltd. Specific examples of hydrogenated liquid polybutadiene (hydrogenated polybutadiene) include BI-2000 and BI-3000 manufactured by Nippon Soda Co., Ltd. In addition, terminal hydroxyl group-modified and hydrogenated liquid polybutadiene (terminal hydroxyl group-modified hydrogenated polybutadiene) specifically includes GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., and the like. be done. Examples of liquid polybutadiene in which an acrylic group is introduced at the terminal (terminal acrylic group-introduced polybutadiene) include TEAI-1000 and TE-2000 manufactured by Nippon Soda Co., Ltd., and the like. Further, examples of the liquid polybutadiene in which an isocyanate group is introduced at the terminal (terminal isocyanate group-introduced polybutadiene) include TP-1001 manufactured by Nippon Soda Co., Ltd., and the like. Further, as a liquid polybutadiene in which a hydroxyl group and a carboxyl group are introduced at the terminal (hydroxyl group/carboxyl group-introduced polybutadiene), specifically, GQ-1000 manufactured by Nippon Soda Co., Ltd. and the like can be mentioned.

Specific examples of the liquid styrene-butadiene rubber include Kuraprene L-SBR-820 and Kuraprene L-SBR-841 manufactured by Kuraray Co., Ltd. Also, Ricon 100, Ricon 181, Ricon 184, etc. manufactured by Clay Valley (USA) can be used.

Examples of the liquid polybutene include NOF polybutene 0N, NOF polybutene 015N, NOF polybutene 3N, NOF polybutene 10N, NOF polybutene 30N, and NOF polybutene 200N manufactured by NOF Corporation. Nisseki Polybutene LV-7, Nisseki Polybutene LV-50, Nisseki Polybutene LV-100, Nisseki Polybutene HV-15, Nisseki Polybutene HV-35, Nisseki Polybutene HV-50 manufactured by JXTG Energy Co., Ltd. , Nisseki polybutene HV-100 and the like.

(Antioxidants, etc.)
In addition to the styrene-isoprene block copolymer and the hydrocarbon resin, the pressure-sensitive adhesive layer preferably contains an antioxidant from the viewpoint of heat deterioration resistance and discoloration prevention. Among them, it is more preferable to use an amine-based or hindered amine-based antioxidant, a phenol-based or hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like, and an amine-based or hindered amine-based antioxidant. It is even more preferred to use a phenolic or hindered phenolic antioxidant, and it is particularly preferred to use a hindered phenolic antioxidant.

The amount of antioxidant used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, in order to improve heat deterioration resistance and discoloration prevention, and 0.5 parts by mass. Part to 1 weight is particularly preferred.

Specific examples of the amine-based antioxidants include ANTAGE OD, ANTAGE DDA, ANTAGE LDA, ANTAGE RD, ANTAGE 3C, ANTAGE 6C, and ANTAGE AW manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.

Specific examples of the hindered amine-based antioxidants include ADEKA Co., Ltd. ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-63P, ADEKA STAB LA-68, ADEKA STAB LA-72, ADEKA STAB LA-77Y, ADEKA STAB LA-81, ADEKA STAB LA-82, ADEKA STAB LA-87, ADEKA STAB LA-402AF, ADEKA STAB LA-502XP and the like.

Specific examples of the phenol-based antioxidant include ANTAGE DAH, ANTAGE DBH, ANTAGE W-300, ANTAGE W-400, ANTAGE W-500, ANTAGE SP and the like manufactured by Kawaguchi Chemical Industry Co., Ltd. Further, Adekastab AO-30, Adekastab AO-40, Adekastab AO-80 and the like manufactured by ADEKA Co., Ltd. may be mentioned.

Specific examples of the hindered phenol-based antioxidant include Adekastab AO-20, Adekastab AO-50, Adekastab AO-60, Adekastab AO-330 manufactured by ADEKA Corporation. In addition, IONOL, IONOL K98, IONOL 220, etc. manufactured by Japan Chemtech Co., Ltd. may be mentioned. IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 56, etc. manufactured by BASF Japan Ltd. can also be mentioned.

Specific examples of the phosphorus-based antioxidants include Adekastab PEP-8, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, manufactured by ADEKA Corporation. ADEKA STAB 3010, ADEKA STAB TPP, and the like. Further, IRGAFOS168 manufactured by BASF Japan Co., Ltd., etc. can be used.

Specific examples of the sulfur-based antioxidant include Adekastab AO-412S and Adekastab AO-503 manufactured by ADEKA Corporation.

In addition to the styrene-isoprene block copolymer and the hydrocarbon resin, the pressure-sensitive adhesive layer contains other polymer components, an ultraviolet absorber, a cross-linking agent, a filler, a pigment, as long as the adhesive strength and peeling resistance are not impaired. Thickeners and the like can be used.

The pressure-sensitive adhesive composition containing the styrene-isoprene block copolymer and the hydrocarbon resin may be a hot-melt type in which the pressure-sensitive adhesive component is heated and melted to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive component is dissolved in an organic solvent for solvent dilution. can be a type. From the viewpoint of heat resistance, a solvent-diluted type can be preferably used.

When the solvent-diluted pressure-sensitive adhesive composition is used, aromatic volatile organic compounds are not substantially used as a solvent from the viewpoint of environmental consideration. Examples of the aromatic volatile organic compounds include toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, benzene, styrene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, n- propylbenzene, cumene, o-ethyltoluene, m-ethyltoluene, p-ethyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2-dimethyl -4-ethylbenzene, 1,3-dimethyl-2-ethylbenzene, 2-propyltoluene, n-butylbenzene, 1,4-bis(1-methylpropyl)benzene and the like. Solvents used in the solvent-diluted pressure-sensitive adhesive composition include aliphatics such as cyclohexane, methylcyclohexane, normal octane, normal heptane, normal hexane, isoprene, normal pentane, isooctane, acetone, methyl ethyl ketone, 2-heptanone, methyl Ketones such as isopropyl ketone, diisopropyl ketone, and diisobutyl ketone, ethers such as tetrahydrofuran, dimethyl ether, and diethyl ether, and esters such as ethyl acetate, butyl acetate, butyl butyrate, and isobutyl butyrate can be used. Particular preference is given to using aliphatics.

The amount of the organic solvent used is preferably 50 parts by mass to 400 parts by mass with respect to 100 parts by mass of the solid content of the adhesive composition in order to adjust the solution viscosity and coating thickness of the adhesive to the desired range. , more preferably 100 to 300 parts by mass, and particularly preferably 150 to 250 parts by mass.

When using the solvent-diluted pressure-sensitive adhesive composition, in order to ensure safety when producing a laminate having a pressure-sensitive adhesive and a pressure-sensitive adhesive layer, for the purpose of antistatic, in addition to the organic solvent, Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol are preferably used.

The amount of the alcohol used can be appropriately adjusted within a range that does not impair the solubility of the pressure-sensitive adhesive composition. 10 parts by mass is more preferable, and 0.5 parts by mass to 5 parts by mass is particularly preferable.

When using the solvent-diluted pressure-sensitive adhesive composition, the solution viscosity can be appropriately adjusted according to the coating method. is preferred, 1,000 mPa·s to 15,000 mPa·s is more preferred, and 4,000 mPa·s to 12,000 mPa·s is particularly preferred.

When the solvent-diluted pressure-sensitive adhesive composition is used, the solid content of the solution can be appropriately adjusted according to storage stability, productivity of the pressure-sensitive adhesive sheet, and thickness of the pressure-sensitive adhesive layer. And from the viewpoint of production efficiency and accuracy of coating thickness, 20% by mass to 60% by mass is preferable, 25% by mass to 50% by mass is more preferable, 30% by mass to 40% by mass is even more preferable, and 32% by mass. to 38% by mass is particularly preferred.

When the solvent-diluted pressure-sensitive adhesive composition is used, the gel fraction of the pressure-sensitive adhesive composition can be appropriately adjusted. , preferably 0% by mass to 60% by mass, more preferably 0% by mass to 40% by mass, even more preferably 0% by mass to 20% by mass, even more preferably 0% by mass to 10% by mass, 0% by mass % to 5% by weight is particularly preferred. In addition, the gel fraction is obtained by measuring the mass (G1) of the coating film of the pressure-sensitive adhesive composition after preparing the coating film of the pressure-sensitive adhesive composition, immersing it in toluene for 24 hours, and then removing it from toluene. It is a value calculated by measuring the mass (G2) of the filtrate (toluene-insoluble matter) dried in a constant temperature bath adjusted to 105° C. after filtering the toluene-insoluble matter.
Gel fraction (% by mass) = (G2/G1) x 100

(Release liner)
As the release liner used in the laminate of the present invention, a substrate such as paper, polyester film, polypropylene film, or polyethylene film provided with a silicone layer can be used. It is preferable to use a material provided with a silicone layer (so-called release paper).

As the substrate of the paper, types such as glassine paper, kraft paper, and fine paper can be preferably used. When the glassine paper is used, a two-layer structure (so-called direct glassine type) in which a silicone layer is provided on the glassine paper can be preferably used. On the other hand, when using kraft paper or high-quality paper, a three-layer structure (so-called resin laminate) is provided with a resin layer such as polyethylene film or polypropylene film as a sealing layer between the paper base material and the silicone layer. Sealing type), or a three-layer structure (so-called resin coat sealing type) in which a coat layer such as polyvinyl alcohol is provided as a sealing layer between a paper substrate and a silicone layer can be preferably used. In addition to keeping the cost of raw materials low, the high strength and heat resistance of the paper substrate makes it possible to dry the adhesive layer under high temperature conditions and efficiently remove volatile organic compounds. , the direct glassine type can be particularly preferably used.

The laminate of the present invention is suitable for use in fixing wire harnesses to headlinings. In addition, due to its excellent tear-resistant strength, heat conductivity, heat diffusion, and shielding properties, it is also used as a hole-filling cap (so-called grommet) for automobile bodies, fixing heater wires, repairing sealing of ducts, heat reflectors, and EMI (electromagnetic interference). It can be suitably used as an electromagnetic wave shielding material for removing interference.

(Preparation example of adhesive for dry lamination)
10 g of aromatic polyisocyanate [trade name: KW-75, manufactured by DIC Corporation] was added to 100 g of polyester polyurethane polyol [trade name: Dick Dry LX-500, manufactured by DIC Corporation], and ethyl acetate was used as a diluting solvent. 210 g of dry laminate adhesive was prepared by adding 100 g and stirring.

(Preparation example 1 of laminated substrate)
On the upper surface of a 50 μm thick aluminum foil [manufactured by UACJ Foil Manufacturing Co., Ltd.], the adhesive for dry lamination was applied in an amount of 4 g / m ² as an adhesive active ingredient (mass after drying), and heated at 85 ° C. After drying for 4 minutes in the environment, a polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, type: LDPE (low-density polyethylene)] is laminated and placed on a nip roll adjusted to 50 ° C. passed. Subsequently, the substrate was cured in an environment of 40° C. for 3 days to prepare a base material (1) in which a polyolefin resin film and a soft metal foil were laminated.

(Preparation example 2 of laminated substrate)
Polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: A-1, thickness: 35 μm, type: LDPE (low-density polyethylene)] was prepared in the same manner as in Preparation Example 1 of Laminated Substrate, in which a polyolefin resin film and a soft metal foil were laminated (2).

(Preparation Example 3 of laminated substrate)
Polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: SB-7, thickness: A base material (3 ) was prepared.

(Preparation Example 4 of laminated substrate)
Polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: AV-51, thickness: A base material (4 ) was prepared.

(Preparation Example 5 of laminated substrate)
Polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] was replaced with a polyethylene film [manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: T.I. U.S.A. X FC-D, thickness: 40 μm, type: LLDPE (linear low-density polyethylene)], in the same manner as in Laminated Substrate Preparation Example 1, a substrate obtained by laminating a polyolefin resin film and a soft metal foil. Material (5) was prepared.

(Preparation Example 6 of laminated substrate)
Polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Toyobo Co., Ltd., trade name: LIX Film LIX-NP L4102 , Thickness: 40 μm, Type: LLDPE (Linear Low Density Polyethylene)] in the same manner as in Laminated Substrate Preparation Example 1, a substrate (6) in which a polyolefin resin film and a soft metal foil are laminated. was prepared.

(Preparation Example 7 of laminated substrate)
Polypropylene film [manufactured by Toyobo Co., Ltd., trade name: Pyrene Film-CT P1111, manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: CT P1111, Thickness: 25 μm, type: CPP (unstretched polypropylene film)] was used in the same manner as in Preparation Example 1 of the laminated substrate, to prepare a substrate (7) in which a polyolefin resin film and a soft metal foil were laminated. .

(Preparation Example 8 of laminated substrate)
Polypropylene film [manufactured by Toyobo Co., Ltd., trade name: Pyrene Film-CT P1111, manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: CT P1111, Thickness: 40 μm, type: CPP (unstretched polypropylene film)] was used in the same manner as in Preparation Example 1 of the laminated substrate, to prepare a substrate (8) in which a polyolefin resin film and a soft metal foil were laminated. .

(Preparation Example 9 of laminated substrate)
Polypropylene film [manufactured by Toyobo Co., Ltd., trade name: Pylen Film-OT P2161, manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film Thickness: 25 μm, type: OPP (biaxially oriented polypropylene film)] was used, in the same manner as in Preparation Example 1 of the laminated substrate, to prepare a substrate (9) in which a polyolefin resin film and a soft metal foil were laminated. did.

(Preparation Example 10 of laminated substrate)
Polypropylene film [manufactured by Toyobo Co., Ltd., trade name: Pylen Film-OT P2161, manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] instead of polyethylene film Thickness: 40 μm, type: OPP (biaxially oriented polypropylene film)] was used, in the same manner as in Preparation Example 1 of the laminated substrate, to prepare a substrate (10) in which a polyolefin resin film and a soft metal foil were laminated. did.

(Preparation Example 11 of laminated substrate)
Polypropylene film [manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: OPU-1] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , thickness: 25 μm, type: OPP (biaxially oriented polypropylene film)], in the same manner as in Laminated Substrate Preparation Example 1, a substrate (11) in which a polyolefin resin film and a soft metal foil are laminated. prepared.

(Preparation Example 12 of laminated substrate)
Polypropylene film [manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: OPU-1] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , thickness: 40 μm, type: OPP (biaxially oriented polypropylene film)], in the same manner as in Laminated Substrate Preparation Example 1, a substrate (12) in which a polyolefin resin film and a soft metal foil are laminated. prepared.

(Preparation Example 13 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN L3501T, thickness: 40 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/configuration: LLDPE/LLDPE/LLDPE] was used to prepare a base material (13) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of a laminated base material.

(Preparation Example 14 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN L3501T, thickness: 50 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/configuration: LLDPE/LLDPE/LLDPE] was used to prepare a base material (14) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of the laminated base material.

(Preparation Example 15 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 30 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , Type/Construction: LLDPE/LLDPE/PP] was used to prepare a base material (15) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Laminated Base Material Preparation Example 1.

(Preparation Example 16 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/structure: LLDPE/LLDPE/PP] was used to prepare a base material (16) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of a laminated base material.

(Preparation Example 17 of laminated substrate)
Multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2150T, thickness: 25 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/configuration: PP/PE/PP] was used to prepare a base material (17) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of the laminated base material.

(Preparation Example 18 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN P2150T, thickness: 40 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/configuration: PP/PE/PP] was used to prepare a base material (18) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of the laminated base material.

(Preparation Example 19 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN P2160T, thickness: 25 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/structure: PP/PP/PP] was used to prepare a base material (19) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of the laminated base material.

(Preparation Example 20 of laminated substrate)
Multi-layer film [manufactured by DIC Corporation, trade name: DIFAREN P2160T, thickness: 40 μm] instead of polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type] , type/configuration: PP/PP/PP] was used to prepare a base material (20) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 1 of the laminated base material.

(Preparation Example 21 of laminated substrate)
Instead of 50 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.], 80 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.] was used, and polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP]. A base material (21) was prepared by laminating a polyolefin-based resin film and a soft metal foil in the same manner as in Preparation Example 1 of a laminated base material, except that these materials were used.

(Preparation Example 22 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2150T, thickness: 40 μm, type/structure: PP/PE/PP] was used to prepare a base material (22) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 21 of a laminated base material.

(Preparation Example 23 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2160T, thickness: 40 μm, type/structure: PP/PP/PP] was used to prepare a base material (23) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 21 of a laminated base material.

(Preparation Example 24 of laminated substrate)
Instead of a 50 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.], a 30 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.] was used, and a polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP]. A base material (24) was prepared by laminating a polyolefin-based resin film and a soft metal foil in the same manner as in Preparation Example 1 of a laminated base material, except that these materials were used.

(Preparation Example 25 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2150T, thickness: 40 μm, type/structure: PP/PE/PP] was used to prepare a base material (25) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 24 of the laminated base material.

(Preparation Example 26 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2160T, thickness: 40 μm, type/structure: PP/PP/PP] was used to prepare a base material (26) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 24 of the laminated base material.

(Preparation Example 27 of laminated substrate)
Instead of 50 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.], 12 μm thick aluminum foil [manufactured by UACJ Foil Co., Ltd.] was used, and polyethylene film [manufactured by Tamapoly Co., Ltd., trade name: V-1, thickness: 30 μm, LDPE (low-density polyethylene) type], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP]. A base material (27) was prepared by laminating a polyolefin-based resin film and a soft metal foil in the same manner as in Preparation Example 1 of a laminated base material, except that these materials were used.

(Preparation Example 28 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2150T, thickness: 40 μm, type/structure: PP/PE/PP] was used to prepare a base material (28) in which a polyolefin resin film and a soft metal foil were laminated in the same manner as in Preparation Example 27 of the laminated base material.

(Preparation Example 29 of laminated substrate)
Instead of the multilayer film [manufactured by DIC Corporation, trade name: DIFAREN R3360T, thickness: 40 μm, type/structure: LLDPE/LLDPE/PP], a multilayer film [manufactured by DIC Corporation, trade name: DIFAREN P2160T, thickness: 40 μm, type/configuration: PP/PP/PP], in the same manner as in Preparation Example 24 of the laminated substrate, to prepare a substrate (29) in which a polyolefin resin film and a soft metal foil were laminated.

(Preparation Example 1 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone R100 [manufactured by Nippon Zeon Co., Ltd., aliphatic hydrocarbon resin, softening point 96 ° C., solid content 100%] 40 g, Pencel D-125 [manufactured by Arakawa Chemical Industries, Ltd., Polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [BASF Japan Co., Ltd. 1 g of Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane [indicated as MCH in the table] were dissolved to prepare 561 g of adhesive composition solution (1). The obtained adhesive composition had a solid content of 35.8% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 2 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone A100 [manufactured by Nippon Zeon Co., Ltd., aliphatic hydrocarbon resin, softening point 100 ° C., solid content 100%] 40 g, Pencel D-125 [manufactured by Arakawa Chemical Industries, Ltd., Polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [BASF Japan Co., Ltd. and 360 g of methylcyclohexane to prepare 561 g of adhesive composition solution (2). The obtained adhesive composition had a solid content of 35.8% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 3 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 40 g, Pencel D-125 [Arakawa Chemical Industry Co., Ltd. Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (3). The obtained adhesive composition had a solid content of 35.8% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 4 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (4). The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 5 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 30 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 551 g of adhesive composition solution (5). The solid content rate of the obtained adhesive composition was 34.7% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 6 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 20 g, Pencel D-125 [Arakawa Chemical Industry Co., Ltd. Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 541 g of adhesive composition solution (6). The solid content rate of the obtained adhesive composition was 33.5% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 7 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 30 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 546 g of adhesive composition solution (7). The solid content rate of the obtained adhesive composition was 34.1% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 8 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] as liquid polybutene, Nisseki Polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] 20 g, IRGANOX1010 [ BASF Japan Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 526 g of adhesive composition solution (8). The solid content rate of the obtained pressure-sensitive adhesive composition was 31.6% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 9 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 30 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 8 g, IRGANOX 1010 [ BASF Japan Co., Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 534 g of adhesive composition solution (9). The solid content rate of the obtained adhesive composition was 32.6% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 10 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-160 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 160 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [BASF Japan ( 1 g of Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (10). The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 11 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-160 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 160 ° C.] 30 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [BASF Japan 1 g of hindered phenolic antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 546 g of pressure-sensitive adhesive composition solution (11). The solid content rate of the obtained adhesive composition was 34.1% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 12 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Tamanol 803L [Arakawa Chemical Industries Co., Ltd. ), terpene phenol, softening point 145 to 160 ° C.] 40 g, as liquid polybutene, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] 20 g, IRGANOX 1010 [BASF Japan ( 1 g of Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (12). The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 13 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As, 35 g of Quintone G100B [manufactured by Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%], YS Polyster T100 [Yasuhara Chemical Co., Ltd. terpene phenol, softening point 100 ° C.] as liquid polybutene, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] 20 g, IRGANOX 1010 [manufactured by BASF Japan Co., Ltd. , hindered phenol-based antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (13). The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 14 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin 35 g of Quintone G100B [manufactured by Nippon Zeon Co., Ltd., aliphatic/aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%], YS Resin SX100 [Yasuhara Chemical Co., Ltd. 40 g of Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene, IRGANOX 1010 [manufactured by BASF Japan Co., Ltd. , hindered phenol-based antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 556 g of adhesive composition solution (14). The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 15 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3270 [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 24% by mass, diblock content 67% by mass, solid content 100%, pellet], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries ( Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] as liquid polybutene, Nisseki Polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] 20 g, IRGANOX1010 [BASF Japan Co., Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 546 g of adhesive composition solution (15). The solid content rate of the obtained adhesive composition was 34.1% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 16 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3520 [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 15% by mass, diblock content 78% by mass, solid content 100%, pellet], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries ( Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] as liquid polybutene, Nisseki Polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] 20 g, IRGANOX1010 [BASF Japan Co., Ltd., Hindered Phenolic Antioxidant] and 360 g of methylcyclohexane were dissolved to prepare 546 g of adhesive composition solution (16). The solid content rate of the obtained adhesive composition was 34.1% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Preparation Example 17 of adhesive composition)
As a styrene-isoprene block copolymer, 100 g of Quintac 3433N [manufactured by Nippon Zeon Co., Ltd., linear structure, styrene content 16% by mass, diblock content 56% by mass, solid content 100%, pellet form], hydrocarbon resin As Quintone G100B [Nippon Zeon Co., Ltd., aliphatic / aromatic copolymer hydrocarbon resin, softening point 100 ° C., solid content 100%] 35 g, Pencel D-125 [Arakawa Chemical Industries Co., Ltd., polymerized rosin ester, softening point 120 to 130 ° C.] 40 g, Nisseki polybutene LV-7 [manufactured by JXTG Energy Co., Ltd., number average molecular weight (Mn) 300] as liquid polybutene 20 g, IRGANOX 1010 [ BASF Japan Co., Ltd., hindered phenol-based antioxidant] was dissolved in 1 g of methylcyclohexane and 10 g of isopropyl alcohol [indicated as IPA in the table] to obtain 556 g of the pressure-sensitive adhesive composition solution (17). prepared. The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Comparative Preparation Example 1 of adhesive composition)
A pressure-sensitive adhesive composition (H1) was prepared in the same manner as in Preparation Example 4 of the pressure-sensitive adhesive composition, except that 360 g of toluene was used instead of 360 g of methylcyclohexane. The solid content rate of the obtained adhesive composition was 35.3% by mass. Moreover, the gel fraction of the obtained adhesive composition was 0% by mass.

(Example 1)
On a release liner [trade name: KA-73G Blue (N7H), manufactured by Lintec Corporation, Direct Glassine], the pressure-sensitive adhesive composition (4) prepared in the above preparation example was applied to a thickness of 40 μm after drying. A sheet having a release liner and a pressure-sensitive adhesive layer was prepared by coating and drying the release liner. Subsequently, the pressure-sensitive adhesive layer was attached to the aluminum foil side of the laminated base material (1) prepared in the above preparation example to obtain a laminate (1).

(Example 2)
A laminate (2) was obtained in the same manner as in Example 1, except that the laminated substrate (2) was used instead of the laminated substrate (1).

(Example 3)
A laminate (3) was obtained in the same manner as in Example 1, except that the laminated substrate (3) was used instead of the laminated substrate (1).

(Example 4)
A laminate (4) was obtained in the same manner as in Example 1, except that the laminated substrate (4) was used instead of the laminated substrate (1).

(Example 5)
A laminate (5) was obtained in the same manner as in Example 1, except that the laminated substrate (5) was used instead of the laminated substrate (1).

(Example 6)
A laminate (6) was obtained in the same manner as in Example 1, except that the laminated substrate (6) was used instead of the laminated substrate (1).

(Example 7)
A laminate (7) was obtained in the same manner as in Example 1, except that the laminated substrate (7) was used instead of the laminated substrate (1).

(Example 8)
A laminate (8) was obtained in the same manner as in Example 1, except that the laminated substrate (8) was used instead of the laminated substrate (1).

(Example 9)
A laminate (9) was obtained in the same manner as in Example 1, except that the laminated substrate (9) was used instead of the laminated substrate (1).

(Example 10)
A laminate (10) was obtained in the same manner as in Example 1, except that the laminated substrate (10) was used instead of the laminated substrate (1).

(Example 11)
A laminate (11) was obtained in the same manner as in Example 1, except that the laminated substrate (11) was used instead of the laminated substrate (1).

(Example 12)
A laminate (12) was obtained in the same manner as in Example 1, except that the laminated substrate (12) was used instead of the laminated substrate (1).

(Example 13)
A laminate (13) was obtained in the same manner as in Example 1, except that the laminated substrate (13) was used instead of the laminated substrate (1).

(Example 14)
A laminate (14) was obtained in the same manner as in Example 1, except that the laminated substrate (14) was used instead of the laminated substrate (1).

(Example 15)
A laminate (15) was obtained in the same manner as in Example 1, except that the laminated substrate (15) was used instead of the laminated substrate (1).

(Example 16)
A laminate (16) was obtained in the same manner as in Example 1, except that the laminated substrate (16) was used instead of the laminated substrate (1).

(Example 17)
A laminate (17) was obtained in the same manner as in Example 1, except that the laminated substrate (17) was used instead of the laminated substrate (1).

(Example 18)
A laminate (18) was obtained in the same manner as in Example 1, except that the laminated substrate (18) was used instead of the laminated substrate (1).

(Example 19)
A laminate (19) was obtained in the same manner as in Example 1, except that the laminated substrate (19) was used instead of the laminated substrate (1).

(Example 20)
A laminate (20) was obtained in the same manner as in Example 1, except that the laminated substrate (20) was used instead of the laminated substrate (1).

(Example 21)
A laminate (21) was obtained in the same manner as in Example 1, except that the laminated substrate (21) was used instead of the laminated substrate (1).

(Example 22)
A laminate (22) was obtained in the same manner as in Example 1, except that the laminated substrate (22) was used instead of the laminated substrate (1).

(Example 23)
A laminate (23) was obtained in the same manner as in Example 1, except that the laminated substrate (23) was used instead of the laminated substrate (1).

(Example 24)
A laminate (24) was obtained in the same manner as in Example 1, except that the laminated substrate (24) was used instead of the laminated substrate (1).

(Example 25)
A laminate (25) was obtained in the same manner as in Example 1, except that the laminated substrate (25) was used instead of the laminated substrate (1).

(Example 26)
A laminate (26) was obtained in the same manner as in Example 1, except that the laminated substrate (26) was used instead of the laminated substrate (1).

(Example 27)
A laminate (27) was obtained in the same manner as in Example 1, except that the laminated substrate (27) was used instead of the laminated substrate (1).

(Example 28)
A laminate (28) was obtained in the same manner as in Example 1, except that the laminated substrate (28) was used instead of the laminated substrate (1).

(Example 29)
A laminate (29) was obtained in the same manner as in Example 1, except that the laminated substrate (29) was used instead of the laminated substrate (1).

(Example 30)
A laminate (30) was obtained in the same manner as in Example 13, except that the pressure-sensitive adhesive composition (4) was applied so as to have a thickness of 60 μm after drying.

(Example 31)
A laminate (31) was obtained in the same manner as in Example 16, except that the pressure-sensitive adhesive composition (4) was applied so as to have a thickness of 60 μm after drying.

(Example 32)
A laminate (32) was obtained in the same manner as in Example 18, except that the pressure-sensitive adhesive composition (4) was applied so that the thickness after drying was 60 μm.

(Example 33)
A laminate (33) was obtained in the same manner as in Example 20, except that the pressure-sensitive adhesive composition (4) was applied so as to have a thickness of 60 μm after drying.

(Example 34)
A laminate (34) was obtained in the same manner as in Example 13, except that the pressure-sensitive adhesive composition (4) was applied so that the thickness after drying was 30 μm.

(Example 35)
A laminate (35) was obtained in the same manner as in Example 16, except that the pressure-sensitive adhesive composition (4) was applied so that the thickness after drying was 30 μm.

(Example 36)
A laminate (36) was obtained in the same manner as in Example 18, except that the pressure-sensitive adhesive composition (4) was applied so that the thickness after drying was 30 μm.

(Example 37)
A laminate (37) was obtained in the same manner as in Example 20, except that the pressure-sensitive adhesive composition (4) was applied so that the thickness after drying was 30 μm.

(Example 38)
A laminate (38) was obtained in the same manner as in Example 14, except that the adhesive composition (1) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 39)
A laminate (39) was obtained in the same manner as in Example 14, except that the adhesive composition (2) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 40)
A laminate (40) was obtained in the same manner as in Example 14, except that the adhesive composition (3) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 41)
A laminate (41) was obtained in the same manner as in Example 14, except that the adhesive composition (5) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 42)
A laminate (42) was obtained in the same manner as in Example 14, except that the adhesive composition (6) prepared in the preparation example was used instead of the adhesive composition (4).

(Example 43)
A laminate (43) was obtained in the same manner as in Example 14, except that the adhesive composition (7) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 44)
A laminate (44) was obtained in the same manner as in Example 14, except that the adhesive composition (8) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 45)
A laminate (45) was obtained in the same manner as in Example 14, except that the adhesive composition (9) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 46)
A laminate (46) was obtained in the same manner as in Example 14, except that the adhesive composition (10) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 47)
A laminate (47) was obtained in the same manner as in Example 14, except that the adhesive composition (11) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 48)
A laminate (48) was obtained in the same manner as in Example 14, except that the adhesive composition (12) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 49)
A laminate (49) was obtained in the same manner as in Example 14, except that the adhesive composition (13) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 50)
A laminate (50) was obtained in the same manner as in Example 14, except that the adhesive composition (14) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 51)
A laminate (51) was obtained in the same manner as in Example 14, except that the adhesive composition (15) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 52)
A laminate (52) was obtained in the same manner as in Example 14, except that the adhesive composition (16) prepared in the above preparation example was used instead of the adhesive composition (4).

(Example 53)
A laminate (53) was obtained in the same manner as in Example 14, except that the adhesive composition (17) prepared in the above preparation example was used instead of the adhesive composition (4).

(Comparative example 1)
A laminate (H1) was obtained in the same manner as in Example 30, except that an aluminum foil having a thickness of 80 μm (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (13).

(Comparative example 2)
A laminate (H2) was obtained in the same manner as in Example 30, except that a 50 μm thick aluminum foil (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (13).

(Comparative Example 3)
A laminate (H3) was obtained in the same manner as in Example 1, except that a 50 μm thick aluminum foil (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (1).

(Comparative Example 4)
A laminate (H4) was obtained in the same manner as in Example 34, except that a 50 μm thick aluminum foil (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (13).

(Comparative Example 5)
A laminate (H5) was obtained in the same manner as in Comparative Example 2, except that the pressure-sensitive adhesive composition (4) was applied so as to have a thickness of 20 μm after drying.

(Comparative Example 6)
A laminate (H6) was obtained in the same manner as in Example 30, except that a 30 μm thick aluminum foil (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (13).

(Comparative Example 7)
A laminate (H7) was obtained in the same manner as in Example 30, except that a 12 μm thick aluminum foil (manufactured by UACJ Foil Corporation) was used instead of the laminate substrate (13).

(Comparative Example 8)
A laminate (H8) was obtained in the same manner as in Example 30, except that a 6.5 μm thick aluminum foil [manufactured by Mitsubishi Aluminum Co., Ltd.] was used instead of the laminate substrate (13).

(Comparative Example 9)
A laminate (H9) was obtained in the same manner as in Comparative Example 1, except that the adhesive composition (H1) prepared in the comparative preparation example was used instead of the adhesive composition (4).

(Comparative Example 10)
A laminate (H10) was obtained in the same manner as in Comparative Example 9, except that the laminated substrate (14) was used instead of the aluminum foil having a thickness of 80 µm.

(Comparative Example 11)
A laminate (H11) was obtained in the same manner as in Example 14, except that the adhesive composition (H1) prepared in the comparative preparation example was used instead of the adhesive composition (4).

(Measurement of cutting strength)
As shown in FIG. 1, the laminates of Examples and Comparative Examples were sampled in a size of 25 mm in width and 50 mm in length, and the release liner was peeled off to form a test piece. . In addition, a nylon string No. 20 (fishing line) was fixed tightly to a jig having the shape shown in FIG. Next, the pedestal and jig shown in FIG. 1 were attached to the lower and upper portions of a tensile tester (compression tester) defined in JIS B7721, respectively. Subsequently, a nylon line was vertically pressed against the test piece at a speed of 50 mm/min, and the strength when the test piece was cut was measured. The unit was recorded in N (Newton). The cutting strength was evaluated according to the following criteria.

Excellent: 55 N or more Excellent: 45 N or more and less than 55 N Good: 40 N or more and less than 45 N Acceptable: 30 N or more and less than 40 N Poor: Less than 30 N

(Measurement of constant load peelability)
The laminates of Examples and Comparative Examples were sampled to a size of 25 mm in width and 150 mm in length, and the release liner was peeled off to form a test piece. After pressing, it was left for 24 hours under an environment of 23° C. and 50% RH. As shown in FIG. 2, 10 mm of one end of the test piece was peeled off, a load (80 g) was applied in the direction of 90°, left for 24 hours, and the peel distance was measured. The unit was recorded in mm. When the peel distance exceeded 140 mm, it was described as ">140". Constant load peelability was evaluated according to the following criteria.

Excellent: Less than 20 mm Excellent: 20 mm or more and less than 40 mm Good: 40 mm or more and less than 50 mm Acceptable: 50 mm or more and less than 100 mm Poor: 100 mm or more

(Measurement of adhesive force)
The laminates of Examples and Comparative Examples were sampled to a size of 25 mm in width and 150 mm in length, and the release liner was peeled off to obtain a test piece. After pressing, it was left for 24 hours under an environment of 23° C. and 50% RH. Using a tensile tester as shown in FIG. 3, the adhesive strength was measured when the test piece was peeled off in the direction of 90° at a speed of 300 mm/min. The unit was recorded in N (Newton). Evaluation was made according to the following criteria.

Excellent: 8N or more Excellent: 6N or more and less than 8N Good: 4N or more and less than 6N Fair: 2N or more and less than 4N Poor: less than 2N

(Evaluation of sticking work aptitude)
The laminates of Examples and Comparative Examples were sampled in a size of 50 mm in width and 100 mm in length, and the release liner was peeled off to form a test piece. As shown in FIG. Two tubes were stacked in a cross shape, and the pressure-sensitive adhesive layer of the test piece was attached to the overlapped portion, and then the test piece was pressed by hand to apply pressure. At that time, the state of breakage of the test piece was observed. The sticking workability was evaluated according to the following criteria.

Hide: The corrugated tube could be properly fixed without breaking neither the aluminum layer nor the polyolefin layer, not only when it was pressed lightly, but also when it was pressed too strongly.
Excellent: Neither the aluminum layer nor the polyolefin layer was torn when lightly pressed, and the corrugated tube was properly fixed. When the pressure was excessively strong, the aluminum layer was slightly torn, but the polyolefin layer was not torn.
Good: Neither the aluminum layer nor the polyolefin layer was torn when lightly pressed, and the corrugated tube was fixed. When pressed strongly at an excessive level, the aluminum layer was severely torn, but the polyolefin layer was not torn.
Acceptable: When lightly pressed, the aluminum layer was torn, but the polyolefin layer was not torn, and the corrugated tube was somehow fixed.
Impossible: Both the aluminum layer and the polyolefin layer were torn when lightly pressed, and the corrugated tube could not be fixed.

(Measurement of volatile organic compounds)
Aromatic volatile organic compounds (toluene, xylene, ethylbenzene) of the laminate according to "Automotive parts - Interior materials - Volatile organic compound emission measurement method" (JASO M902) stipulated by the Society of Automotive Engineers of Japan (JASO) 3 components) was measured.

First, nitrogen gas was sealed in a Tedlar bag with a volume of 10 L, then heated for a long time, and then the operation of removing the nitrogen gas from the Tedlar bag was repeated several times, and N, N-dimethylacetamide and phenol were at levels at which they were not detected as blank components. The inside of the Tedlar bag was washed until Subsequently, the laminates of Examples and Comparative Examples were cut into pieces each having a width of 100 mm and a length of 100 mm. The test piece was enclosed in the washed Tedlar bag, filled with nitrogen gas, and then the nitrogen gas was removed, which was repeated twice. Subsequently, using an integrating rheometer, the Tedlar bag was filled with 5 L of nitrogen gas, and the cock of the Tedlar bag was closed. The Tedlar bag was placed in an oven adjusted to 65° C. and heated for 2 hours.

After that, 1 L of the sample gas was sampled into the TenaxTA adsorption tube at an air sampling rate of 0.2 L/min while the temperature was maintained at 65°C. After collection, the adsorption tube was subjected to a thermal desorption gas chromatograph/mass spectrometer (GC/MS) to measure the amount of aromatic volatile organic compounds (three components of toluene, xylene, and ethylbenzene) emitted. The amount generated was calculated using a calibration curve of standard substances of the specified three components. When it is below the lower limit (0.05 μg) that can be quantitatively measured, it is described as “ND”. Evaluation was made according to the following criteria.

Hide: None of the three designated components was "ND" (Not Detected).
Excellent: At least one of the specified three components was at a detectable level, and the measured value was less than 1 µg/unit.
Good: At least one of the specified three components was at a detectable level, and the measured value was less than 10 µg/unit.
Acceptable: At least one of the three specified components was at a detectable level, and the measured value was less than 1,000 μg (1 mg)/unit.
Impossible: At least one of the specified three components was at a detectable level, and the measured value was 1,000 μg (1 mg)/unit or more.

1 Frame 2 Jig 3 Nylon Teg 4 Test Piece 5 Head Lining 6 Load 7 Chuck of Tensile Tester 8 Corrugated Tube

Claims (16)

A laminate having an adhesive layer on at least one side of a substrate directly or via another layer, wherein the substrate is a substrate obtained by laminating a polyolefin resin film and a soft metal foil, and the adhesive the layer contains a styrene-isoprene block copolymer and a hydrocarbon resin and is substantially free of aromatic volatile organic compounds as a solvent ;
A laminate, wherein the olefin-based resin film is a multi-layer film obtained by combining polyolefins of different compositions . 2. The laminate according to claim 1, wherein said olefinic resin film is a multi-layer film obtained by combining polyethylene or polypropylene of different compositions . 3. The laminate according to claim 1, wherein the olefinic resin film is a multi-layer film in which polyethylene and polypropylene are combined. The laminate according to any one of claims 1 to 3 , wherein the soft metal foil is an aluminum foil. 5. The laminate according to any one of claims 1 to 4 , wherein the olefin resin film and the soft metal foil are laminated by a dry lamination method. The laminate according to any one of claims 1 to 5 , wherein the styrene-isoprene block copolymer has a styrene content in the range of 10% by mass to 50% by mass. The laminate according to any one of claims 1 to 6 , wherein the styrene-isoprene block copolymer has a diblock content in the range of 10% to 80% by weight. The laminate according to any one of claims 1 to 7 , wherein the hydrocarbon resin is an aliphatic/aromatic copolymer hydrocarbon resin. The laminate according to any one of claims 1 to 8 , wherein the hydrocarbon resin has a softening point in the range of 80°C to 150°C. 10. The mass ratio of the content of the styrene-isoprene block copolymer and the hydrocarbon resin (styrene-isoprene block copolymer/hydrocarbon resin) is in the range of 0.5-20 . laminate. Any one of claims 1 to 10 , wherein the pressure-sensitive adhesive layer contains one or more tackifying resins selected from the group consisting of rosin-based resins, terpene-based resins, styrene-based resins, chroman resins, and xylene resins. The laminate according to the item. The laminate according to any one of claims 1 to 11 , wherein the amount of the tackifying resin used is 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the styrene-isoprene block copolymer. The laminate according to any one of claims 1 to 12 , wherein the tackifying resin has a softening point of 100°C to 180°C. 14. The laminate according to any one of claims 1 to 13, further comprising a release liner, said release liner being of the direct glassine type. Emissions of toluene, xylene, and ethylbenzene measured according to "Automotive parts - Interior materials - Volatile organic compound emission measurement method" (JASO M902) stipulated by the Society of Automotive Engineers of Japan (JASO) are all less than 1 mg/unit. The laminate according to any one of claims 1 to 14, characterized in that 16. The laminate according to any one of claims 1 to 15, which is used for fixing an automotive assembly wire to a molded ceiling.

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