TW201946994A - Adhesive sheet which is a heat-peelable adhesive tape including a substrate and an adhesive layer - Google Patents

Abstract

The invention provides an adhesive sheet, which is a heat-peelable adhesive tape including a substrate and an adhesive layer, wherein the adhesive layer is prevented from being affected by heat applied from the substrate side so as not to deteriorate even being subject to a roll-to-roll process. The adhesive sheet according to the present invention includes a first adhesive layer, a first base material, a second adhesive layer, and a second base material in sequence. The first adhesive layer and the first base material constitute a heat-peelable adhesive tape, and the second adhesive layer and the second base material constitute a laminated portion A. The laminated portion A is disposed to be peelable from the heat-peelable adhesive tape.

Description

Adhesive sheet

The present invention relates to an adhesive sheet.

It is known as an adhesive tape used for the purpose of temporarily fixing a processed product in the steps of manufacturing electronic parts, etc., that exhibits adhesiveness during temporary fixation and peelability by heating without fixing. Such an easily peelable adhesive tape (for example, Patent Document 1). Such an adhesive tape usually includes a substrate and an adhesive layer provided on the substrate. In addition, in the case of manufacturing the above-mentioned adhesive tape, after the base material and the adhesive are laminated to form a laminated body, the laminated body may be used in an inspection step and an adhesive layer processing step. In such a step, a so-called roll-to-roll process in which the above-mentioned laminated body is conveyed by a conveying roller is mostly used. At this time, frictional heat is generated due to contact with the conveying roller or the like, and the characteristics of the adhesive layer are deteriorated.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-131507

[Problems to be solved by the invention]

The present invention has been made in order to solve the foregoing problems, and an object thereof is to provide an adhesive sheet having a heat-peeling type adhesive tape having a substrate and an adhesive layer, and the adhesive layer is not easily applied from the substrate side. The influence of the heat, even if used in the roll-to-roll process, the adhesive layer is not easy to deteriorate.
[Technical means to solve the problem]

The adhesive sheet of the present invention includes a first adhesive layer, a first substrate, a second adhesive layer, and a second substrate in this order. The first adhesive layer and the first substrate constitute a heat-peelable adhesive tape. The second adhesive layer and the second base material constitute a laminated portion A, and the laminated portion A is disposed so as to be peelable from the heat-peelable adhesive tape.
In one embodiment, the thickness of the laminated portion A is 10 μm or more.
In one embodiment, the gel fraction of the second adhesive layer is 20% to 100% by weight.
In one embodiment, the adhesion force A2 of the laminated portion A to the polyethylene terephthalate film after being heated at 100 ° C. for 30 minutes relative to the laminated portion A to the polyethylene terephthalate film. The normal adhesive force A1 is 10 times or less.
In one embodiment, the normal adhesion A1 of the laminated portion A to the polyethylene terephthalate film is 0.05 N / 20 mm to 5 N / 20 mm.
According to another aspect of the present invention, a method for transferring a heat-peelable adhesive tape is provided. The transfer method is a transfer method of a heat-peeling type adhesive tape including a first substrate and a first adhesive layer, and the transfer method includes: laminating a laminated portion A on the first substrate side, and laminating a laminated portion A The heat-peelable adhesive tape is conveyed.
[Effect of the invention]

According to the present invention, it is possible to provide an adhesive sheet having a heat-peeling type adhesive tape having a substrate and an adhesive layer, and the adhesive layer is not easily affected by the heat applied from the substrate side, even if it is provided for roll-to-roll In the manufacturing process, the adhesive layer is not easy to deteriorate.

A. The overall composition of the adhesive sheet
FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. The adhesive sheet 100 includes a first adhesive layer 11, a first substrate 12, a second adhesive layer 21, and a second substrate 22 in this order. The first adhesive layer 11 and the first base material 12 constitute a heat-peelable adhesive tape 10. The second adhesive layer 21 and the second base material 22 constitute a laminated portion A20. The laminated part A20 is arrange | positioned so that it may peel from the thermal peeling-type adhesive tape 10. Although not shown, the adhesive sheet may further include any appropriate other layers.

In the present invention, by providing a build-up portion A20 on the first base material 12 side of the heat-peelable pressure-sensitive adhesive tape 10, the first adhesive layer 11 can be protected from the first base material 12 side (substantially the build-up portion A20). Side) Heat applied. More specifically, when it is necessary to supply the heat-peelable adhesive tape 10 to a roll-to-roll process (for example, inspection of the adhesive layer, processing of the adhesive layer, etc.), the heat-peelable adhesive tape 10 is attached with The form of the heat-peeling type adhesive tape 10 (that is, the adhesive sheet 100) of the laminated portion A20 disposed on the first substrate 12 side is provided for this process, thereby protecting the first adhesive layer 11 from being caused by contact with the transfer roller. Effects such as friction cause temperature rise. When the heat-peelable adhesive tape 10 is completed through a specific step, the laminated portion A20 is peeled off, and the heat-peelable adhesive tape 10 can be used, for example, as a temporary fixing tape in the manufacturing process of an electronic component. According to the present invention, by providing the build-up portion A20 which is laminated in a peelable manner, it is possible to prevent thermal deterioration of the adhesive layer (that is, the first adhesive layer) of the heat-peelable pressure-sensitive adhesive tape 10 and can be used as a heat-peelable type of adhesive. The band 10 is made to a suitable thickness according to the actual use. The heat-peelable pressure-sensitive adhesive tape 10 may be stored in the form of the heat-peelable pressure-sensitive adhesive tape 10 (that is, the adhesive sheet 100) of the buildup portion A20 before being used.

In one embodiment, the adhesive sheet may be provided in a strip shape.

B. Thermal peeling type adhesive tape
The heat-peeling type adhesive tape has a characteristic of reducing or disappearing the adhesive force by heating. The form of such a heat-peelable adhesive tape is not particularly limited, and examples thereof include a tape having an adhesive layer containing thermally expandable microspheres, and a tape having a heat-curable adhesive layer. When using the heat-peelable pressure-sensitive adhesive tape, for example, when processing electronic parts (such as ceramic capacitors) or when temporarily fixing a processed product, when performing specific processing on the processed product, the adhesiveness required for temporary fixing is exhibited When the heat-peeling type adhesive tape is peeled from the processed object after processing, the adhesive force is reduced or disappeared by heating to show good peelability. In one embodiment, the heat-peelable pressure-sensitive adhesive tape includes a substrate (first substrate) and an adhesive layer (first adhesive layer) containing an adhesive A and a thermally expandable microsphere. Hereinafter, as a representative example of the heat-peelable pressure-sensitive adhesive tape, a heat-peelable pressure-sensitive adhesive tape having a first adhesive layer containing thermally expandable microspheres will be described.

The thermally expandable microspheres in the first adhesive layer can foam at a specific temperature. For such an adhesive layer containing heat-expandable microspheres, the heat-expandable microspheres are foamed by heating, thereby causing unevenness on the adhesive surface (that is, the surface of the first adhesive layer), and the adhesive force is reduced or disappeared.

The adhesive force (before heating) of the heat-peelable adhesive tape to a polyethylene terephthalate film (for example, 25 μm in thickness) is preferably 0.1 N / 20 mm or more, and more preferably 1.0 N / 20 mm to 50 N / 20 mm, more preferably 2.0 N / 20 mm to 20 N / 20 mm. Within this range, for example, a heat-peelable pressure-sensitive adhesive tape useful as a sheet for temporary fixing used in the manufacture of electronic parts can be obtained. Adhesive force in this specification is measured by a method in accordance with JIS Z 0237: 2000 at 23 ° C (adhesion conditions: 2 kg roller reciprocating once, peeling speed: 300 mm / min, peeling angle 180 °) Adhesion.

The adhesive force of the heat-peelable adhesive tape on the polyethylene terephthalate film is preferably 0.2 N / 20 mm or less, and more preferably 0.1 N / 20 mm or less. In the present specification, the heating of the heat-peelable adhesive tape refers to heating at a temperature and time where the thermally expandable microspheres expand or foam to reduce the adhesive force. This heating is, for example, heating at 70 ° C to 270 ° C for 1 minute to 10 minutes.

The thickness of the thermal peeling type adhesive tape is preferably 30 μm to 500 μm, and more preferably 40 μm to 300 μm.

B-1. First adhesive layer The thickness of the first adhesive layer is preferably 1 μm to 30 μm, more preferably 1 μm to 20 μm, and even more preferably 1 μm to 10 μm. Within this range, a heat-peelable pressure-sensitive adhesive tape capable of preventing positional displacement of the adherend and sinking into the first adhesive layer can be obtained. The thickness of each layer constituting the adhesive sheet can be measured using a ruler, a vernier caliper, and a micrometer. Microscopes such as an electron microscope, an optical microscope, and an atomic force microscope can also be used. Furthermore, the interface of adjacent layers can be discriminated according to the difference in composition, and the thickness of each layer can be measured. Examples of interface discrimination methods include Raman spectroscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy; matrix-assisted laser desorption free time-of-flight mass spectrometer (MALDI-TOFMS) or time-of-flight secondary ions Mass spectrometer (TOF-SIMS) and other mass analysis methods.

The elastic modulus of the first adhesive layer obtained by the nanoindentation method at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and still more preferably 0.1 MPa to 10 MPa. Within this range, a heat-peelable pressure-sensitive adhesive tape capable of preventing positional displacement of the adherend and sinking into the first adhesive layer can be obtained. The elastic modulus obtained by the nanoindentation method refers to the continuous measurement of the load and indentation depth of the indenter when the indenter is pressed into the sample (such as the adhesive surface) under load and unloading. Elastic modulus obtained from the obtained load-indentation depth curve. In this specification, the elastic modulus obtained by the nanoindentation method means that the measurement conditions are set to load: 1 mN, load, unloading speed: 0.1 mN / s, holding time: 1 s and measured in the manner described above. Modulus of elasticity. When the first adhesive layer includes thermally expandable microspheres, the elastic modulus of the first adhesive layer obtained by the nanoindentation method is to select a portion where no thermally expandable microspheres are present and use the above measurement. The elastic modulus measured by the method.

(Adhesive A)
As the adhesive A constituting the first adhesive layer, any appropriate adhesive can be used as long as the effect of the present invention can be obtained. In one embodiment, as the adhesive A, a hardening type adhesive is used, and an active energy ray hardening type adhesive is preferably used. In another embodiment, a pressure-sensitive adhesive is used as the adhesive A. Examples of the pressure-sensitive adhesive include acrylic adhesives and rubber-based adhesives.

(Active energy ray hardening adhesive)
Examples of the resin material constituting the active energy ray-curable adhesive include an ultraviolet curing system (Kato Kiyoshi, published by the Comprehensive Technology Center, (1989)), a photocuring technique (Technical Information Association (2000)), Japan Resin materials described in Patent Publication No. 2003-292916, Japanese Patent No. 4151850, and the like. More specifically, a resin material (R1) containing a polymer as a base agent and an active energy ray reactive compound (monomer or oligomer), and a resin material (R2) containing an active energy ray reactive polymer may be mentioned. Wait.

Examples of the polymer used as the base agent include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, and butyl rubber. , Polyisobutylene rubber, nitrile rubber (NBR) and other rubber-based polymers; silicone polymers; acrylic polymers. These polymers can be used alone or in combination of two or more.

Examples of the active energy ray-reactive compound include a photoreactive monomer having a plurality of functional groups having a carbon-carbon multiple bond, such as acrylfluorenyl, methacrylfluorenyl, vinyl, allyl, and ethynyl. Or oligomers. Among them, a compound having an ethylenically unsaturated functional group is preferably used, and a (meth) acrylic compound having an ethylenically unsaturated functional group is more preferably used. Since a compound having an ethylenically unsaturated functional group easily generates radicals by using ultraviolet rays, if the compound is used, a first adhesive layer that can harden in a short time can be formed. In addition, if a (meth) acrylic compound having an ethylenically unsaturated functional group is used, an adhesive layer having a moderate hardness (specifically, a hardness in which the thermally expandable microspheres can foam well) can be formed after curing. . Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and pentaerythritol tri (meth) acrylic acid. Ester, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, (meth) acrylate urethane-based compounds and other compounds containing (meth) acrylfluorenyl groups; the Contains (meth) acrylic fluorenyl-based compounds pentamers, etc. These compounds can be used alone or in combination of two or more.

In addition, as the active energy ray reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinylsiloxane; or oligomers composed of the monomers can also be used. . The resin material (R1) containing these compounds can be hardened by high energy rays such as ultraviolet rays and electron beams.

Further, as the active energy ray-reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule can be used. Regarding this mixture, by irradiation of active energy rays (for example, ultraviolet rays, electron beams), organic salts are cleaved to generate ions, which become the starting species and cause ring-opening reactions of heterocycles to form a three-dimensional network structure. Examples of the organic salts include iodonium salts, sulfonium salts, antimony salts, sulfonium salts, and borate salts. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, oxetane, oxolane, ethanesulfide, and aziridine.

In the above-mentioned resin material (R1) containing the polymer as the mother agent and the active energy ray reactive compound, the content ratio of the active energy ray reactive compound is preferably 0.1 part by weight relative to 100 parts by weight of the polymer as the mother agent. ~ 500 parts by weight, more preferably 1 to 300 parts by weight, and still more preferably 10 to 200 parts by weight.

Examples of the active energy ray-reactive polymer include polymerization of an active energy ray-reactive functional group having a carbon-carbon multiple bond, such as an acryl group, a methacryl group, a vinyl group, an allyl group, or an ethynyl group. Thing. It is preferable to use a compound (polymer) having an ethylenically unsaturated functional group, and it is more preferable to use a (meth) acrylic polymer having an acrylfluorene group or a methacrylfluorene group. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate and the like.

The resin material (R2) containing the active energy ray reactive polymer may further contain the active energy ray reactive compound (monomer or oligomer).

The above-mentioned active energy ray-curable adhesive can be hardened by irradiation with active energy rays. In the heat-peelable pressure-sensitive adhesive tape, after the adherend is adhered before the adhesive A is cured, the active energy ray is irradiated to harden the adhesive A, whereby the adherend can be closely adhered. Examples of active energy rays include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio frequency waves, alpha rays, beta rays, electron beams, plasma flow, ionizing rays, and particle rays. The conditions such as the wavelength and irradiation amount of the active energy ray can be set to any appropriate conditions depending on the type of the resin material used and the like. For example, it is possible to irradiate ultraviolet rays with an irradiation amount of 10 to 1000 mJ / cm ^{2 to} harden the adhesive A.

(Acrylic Adhesive)
Examples of the acrylic adhesive include acrylic polymer (homopolymer or copolymer) using one or two or more alkyl (meth) acrylates as monomer components as a base polymer. Acrylic adhesives, etc. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( Butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, hex (meth) acrylate Ester, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) ) Isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Tridecyl ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, C1-20 alkyl (meth) acrylates, such as octadecyl (meth) acrylate, undecyl (meth) acrylate, and eicosyl (meth) acrylate. Among them, an alkyl (meth) acrylate having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used.

In order to improve the cohesive force, heat resistance, and crosslinkability, the acrylic polymer may include a unit corresponding to other monomer components that can be copolymerized with the alkyl (meth) acrylate, as necessary. Examples of such monomer components include carboxyl-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, iconic acid, maleic acid, fumaric acid, and crotonic acid; Anhydride monomers, such as Iconic anhydride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, (meth) acrylic acid Hydroxyl octyl ester, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate and other hydroxyl-containing monomers; styrene sulfonic acid, allyl Sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylamidonaphthalene Sulfonic group-containing monomers such as sulfonic acid; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxymethyl (N-substituted) fluorenamide-based monomers such as (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N (meth) acrylic acid, N-dimethylaminoethyl, (methyl) (Meth) acrylic acid amine alkyl ester monomers such as tert-butylamino ethyl methacrylate; methethyl (meth) acrylate, ethoxy ethyl (meth) acrylate, etc. ) Alkoxyalkyl acrylate monomers; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide Maleimide monomers such as imine; N-methyl Ikonimide, N-ethyl Ikonimide, N-butyl Ikonimide, N-octyl Ikonimide Amine, N-2-ethylhexyl Ikonimide, N-cyclohexyl Ikonimide, N-Lauryl Ikonimide, and other Ikonimide monomers; N- (methyl) Acrylic acid oxymethylene succinimide, N- (meth) acryl fluorenyl-6-oxohexamethylene succinimide, N- (meth) acryl fluorenyl-8-oxyoctamethylene Succinimide-based monomers such as succinimide; vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, ethylene Is pyrimidine, vinyl piperazine, vinylpyridine, vinylpyrrole, vinylimidazole, vinyloxazole, vinyl? , Vinyl monomers such as N-vinylcarboxamides, styrene, α-methylstyrene, N-vinyl caprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxyethylene glycol (meth) acrylate Diol-based acrylate monomers such as methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate, etc. Acrylic monomers such as rings, halogen atoms, and silicon atoms; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylic acid Ester, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (methyl) Base) polyfunctional monomers such as acrylate, epoxy acrylate, polyester acrylate, acrylic urethane; isoprene, butadiene , Isobutylene and other olefinic monomers; vinyl ether vinyl ether-based monomers. These monomer components can be used individually or in combination of 2 or more types.

(Rubber-based adhesive)
Examples of the rubber-based adhesive include natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, and styrene-isoprene Styrene · styrene block copolymer (SIS) rubber, styrene · butadiene · styrene block copolymer (SBS) rubber, styrene · ethylene · butene · styrene block copolymer (SEBS) rubber, Styrene, ethylene, propylene, and styrene block copolymer (SEPS) rubber, styrene, ethylene, and propylene block copolymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, and modified materials thereof Rubber-based adhesives such as synthetic rubber as the base polymer.

(additive)
The said adhesive agent A can contain arbitrary appropriate additives as needed. Examples of the additives include initiators, crosslinking agents, adhesion-imparting agents, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, Peeling modifiers, softeners, surfactants, flame retardants, antioxidants, etc.

(Thermally expandable microspheres)
In one embodiment, the first adhesive layer includes thermally expandable microspheres. The first adhesive layer containing the heat-expandable microspheres expands or foams by heating to expand the heat-expandable microspheres. As a result, unevenness is generated on the adhesive surface, and the adhesive force is reduced or disappeared. When a heat-peeling type adhesive tape having such a first adhesive layer is used as a temporary fixing material, the adherend after the temporary fixing can be easily peeled off.

As the thermally expandable microspheres, any appropriate thermally expandable microspheres can be used as long as they are expandable or foamable microspheres by heating. As the thermally expandable microspheres, for example, microspheres obtained by encapsulating a substance that is easily expanded by heating in a shell having elasticity can be used. Such thermally expandable microspheres can be produced by any appropriate method, such as a coacervation method and an interfacial polymerization method.

Examples of substances that can be easily expanded by heating include propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, heptane, Low boiling point liquids such as octane, petroleum ether, halides of methane, and tetraalkylsilane; azodimethoxamine gasified by thermal decomposition.

Examples of the material constituting the shell include: nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, and Ikon Acid, maleic acid, fumaric acid, citraconic acid and other carboxylic acid monomers; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, beta β -(Meth) acrylates such as carboxyethyl esters; styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; acrylamide, substituted acrylamide, methacrylamide, substituted methacryl A polymer composed of an ammonium monomer such as amidine. The polymer composed of these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and methyl methacrylate-acrylonitrile copolymer. , Acrylonitrile-methacrylonitrile-itaconic acid copolymer, etc.

As the thermally expandable microspheres, an inorganic foaming agent or an organic foaming agent may be used. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and various azides. Examples of the organic blowing agent include chlorofluorinated alkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethylformamide, and azodicarboxylate. Azo compounds such as barium acid; p-toluenesulfonylhydrazine, diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis (benzenesulfonylhydrazine), allylbis (sulfonium Hydrazine) and other hydrazine-based compounds; p-tolylsulfonamidourea, 4,4'-oxobis (benzenesulfonamidourea) and other aminourea-based compounds; 5-morpholinyl-1,2,3, Triazole compounds such as 4-thiatriazole; N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroso-p-xylylenediamine N-nitroso compounds such as amines.

As the thermally expandable microsphere, a commercially available product may be used. Specific examples of commercially available thermally expandable microspheres include the product name "Matsumoto Microsphere" (grades: F-30, F-30D, F-36D, F-36LV, F -50, F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), products made by Japan Fillite Name "Expancel" (Class: 053-40, 031-40, 920-40, 909-80, 930-120), "DAIFOAM" (Class: H750, H850, H1100, S2320D) manufactured by Wu Yu Chemical Industry Co., Ltd. , S2640D, M330, M430, M520), "ADVANCELL" (Grade: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501) manufactured by Sekisui Chemical Industry Co., Ltd.

The particle diameter of the thermally expandable microspheres before heating is preferably 0.5 μm to 80 μm, more preferably 5 μm to 45 μm, still more preferably 10 μm to 20 μm, and even more preferably 10 μm to 15 μm. Therefore, when the average particle diameter is used to describe the particle size of the thermally expandable microspheres before heating, it is preferably 6 μm to 45 μm, and more preferably 15 μm to 35 μm. The particle diameter and the average particle diameter are values obtained by a particle size distribution measurement method in a laser scattering method.

The thermally expandable microspheres preferably have a moderate strength that does not break until the volume expansion rate is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more. When such a thermally expandable microsphere is used, it is possible to efficiently reduce the adhesive force by heat treatment.

The content ratio of the heat-expandable microspheres in the first adhesive layer can be appropriately set depending on the required reduction of the adhesive force and the like. The content ratio of the heat-expandable microspheres is 100 parts by weight with respect to 100 parts by weight of the base polymer forming the first adhesive layer, for example, 1 to 150 parts by weight, preferably 10 to 130 parts by weight, and more preferably 25 parts by weight Parts ~ 100 parts by weight.

B-2. First substrate As the first substrate, for example, resin sheet, non-woven fabric, paper, metal foil, woven fabric, rubber sheet, foamed sheet, laminates of these (especially including resin sheet) Laminated body) and so on. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene (PE). ), Polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamide (aromatic polyamide), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine-based resin, polyetheretherketone (PEEK), and the like. Examples of the nonwoven fabric include nonwoven fabrics obtained from natural fibers having heat resistance such as nonwoven fabric including Manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabric, polyethylene resin nonwoven fabric, and ester resin nonwoven fabric.

The thickness of the first substrate can be set to any appropriate thickness according to the required strength or flexibility, the purpose of use, and the like. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, even more preferably 3 μm to 300 μm, and most preferably 5 μm to 250 μm.

The first substrate may be surface-treated. Examples of the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment using a primer. Such surface treatment can improve the adhesion between the first adhesive layer and the substrate. In particular, a coating treatment using an organic coating material is preferable in terms of improving the adhesion and preventing the first adhesive layer from being easily damaged when peeling. The surface treatment layer may be formed on a surface on the side of the first adhesive layer.

Examples of the organic coating material include materials described in Plastic Hard Coating Material II (CMC Publication, (2004)). It is preferable to use a urethane-based polymer, and it is more preferable to use a polyacrylate urethane, a polyester urethane, or a precursor thereof. The reason is that the application and application of the base material are simple, industrially, a variety of substances can be selected, and they can be obtained at low cost. The urethane-based polymer is, for example, a polymer containing a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl-containing acrylic compound or a hydroxyl-containing ester compound). The organic coating material may contain a chain extender such as a polyamine, an aging inhibitor, an oxidation stabilizer, and the like as optional additives. The thickness of the organic coating layer is not particularly limited. For example, it is preferably about 0.1 μm to 10 μm, preferably about 0.1 μm to 5 μm, and more preferably about 0.5 μm to 5 μm. The organic coating layer can be formed using, for example, any appropriate printing method on the organic coating material.

B-3. The intermediate layer heat-peelable pressure-sensitive adhesive tape may further include an intermediate layer between the first adhesive layer and the first substrate. Examples of the material constituting the intermediate layer include silicone polymers, epoxy polymers, polycarbonate polymers, vinyl polymers, acrylic polymers, urethane polymers, and the like. Polymer materials such as polyester-based polymers, polyolefin-based polymers, polyamide-based polymers, polyimide-based polymers, and unsaturated hydrocarbon-based polymers. If such a polymer material is used, the type of monomer, the cross-linking agent, the degree of polymerization, and the like are appropriately selected so that an intermediate layer having the above-mentioned elastic modulus can be easily formed. These polymer materials may be used alone or in combination of two or more.

In one embodiment, as the material constituting the intermediate layer, a resin material that can be hardened by irradiation with active energy rays is used. If a resin material that can be hardened by irradiation with active energy rays is used, the active energy rays are irradiated at an appropriate timing, so that the elastic modulus of the intermediate layer can be improved, and the adjustment of the elastic modulus becomes easy. If an intermediate layer is formed using such a material, the elasticity is low, the flexibility is high, and the handleability is excellent when the adhesive sheet is attached. After the attachment, the active energy ray can be irradiated to obtain the adjustable range. The elastic modulus of the adhesive sheet.

Examples of the resin material that can be hardened by irradiation with active energy rays include, for example, those described in the above item B-1, which include a polymer as a base agent and an active energy ray-reactive compound (monomer or oligomer). Resin material (R1), resin material (R2) containing an active energy ray reactive polymer, and the like. In one embodiment, as the active energy ray reactive compound in the resin material (R1) used as the material of the intermediate layer, a compound having an ethylenically unsaturated functional group can be used. Moreover, in one embodiment, as the active energy ray reactive polymer in the resin material (R2), a compound (polymer) having an ethylenically unsaturated functional group can be used.

As the material constituting the intermediate layer, a hot-melt resin made of a thermoplastic resin such as an ethylene-vinyl acetate copolymer, a polypropylene-based resin, or a polyamide-based resin can be used.

The intermediate layer may further include any appropriate additive as necessary. Examples of the additives include initiators, crosslinking agents, adhesion-imparting agents, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, Peeling modifiers, softeners, surfactants, flame retardants, antioxidants, etc.

The thickness of the intermediate layer is preferably 1 μm to 200 μm, more preferably 5 μm to 50 μm, and still more preferably 10 μm to 40 μm.

C. Layer A
As described above, the laminated portion A includes the second adhesive layer and the second substrate. The adhesive layer is generally less thermally conductive than the substrate. In the present invention, since the laminated portion A including such an adhesive layer (second adhesive layer) is used to protect the heat-peelable adhesive tape, the first adhesive layer (the adhesive layer of the heat-peelable adhesive tape) can be prevented. ) 'S thermal degradation.

The adhesion A1 (normal adhesion A1) of the laminated portion A to a polyethylene terephthalate film (for example, 50 μm in thickness) is preferably 0.04 N / 20 mm to 10 N / 20 mm, and more preferably 0.05. N / 20 mm ~ 5 N / 20 mm, further preferably 0.08 N / 20 mm ~ 4.5 N / 20 mm, further preferably 0.1 N / 20 mm ~ 2.5 N / 20 mm, particularly preferably 0.15 N / 20 mm ~ 1.2 N / 20 mm. Within this range, it is possible to obtain an adhesive sheet (that is, a laminated body of the above-mentioned heat-peelable adhesive tape and the laminated portion A) in a specific step when the laminated portion A is not easily peeled from the heat-peelable adhesive tape, After the step, the unnecessary laminated layer A can be easily peeled off from the heat-adhesive type adhesive tape.

After the laminated part A is heated at 100 ° C. for 30 minutes, the adhesive force A2 (adhesive force A2 after heating) on the polyethylene terephthalate film (for example, 50 μm in thickness) is preferably 0.05 N / 20 mm ~ 10.0 N / 20 mm, more preferably 0.08 N / 20 mm to 5.0 N / 20 mm, and still more preferably 0.10 N / 20 mm to 1.5 N / 20 mm. If it is this range, the laminated part A can have a required peeling force even if the temperature of the adhesive sheet rises when the adhesive sheet is supplied to a specific step. In addition, the adhesive force after heating is the adhesive force at 23 ° C when the temperature of the second adhesive layer is reduced to 23 ° C after heating at the above temperature.

The above-mentioned heating adhesion A2 is preferably 10 times or less, more preferably 5 times or less, more preferably 0.001 times to 2.5 times, and even more preferably 0.001 times to 1.8 times, compared to the normal state adhesion A1. If it is this range, the laminated part A can have a required peeling force even if the temperature of the adhesive sheet rises when the adhesive sheet is supplied to a specific step.

The thickness of the laminated part A is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, particularly preferably 50 μm to 500 μm, and most preferably 50 μm to 300 μm. When the thickness of the laminated portion A is 10 μm or more, thermal degradation of the first adhesive layer can be significantly prevented.

C-1. Second adhesive layer The thickness of the second adhesive layer is preferably 1 μm to 100 μm, more preferably 5 μm to 80 μm, and still more preferably 5 μm to 50 μm. Within this range, thermal degradation of the first adhesive layer can be significantly prevented.

The second adhesive layer is typically an adhesive B containing a specific polymer as a base polymer. As the adhesive B, it is also preferable to use a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive used in the second adhesive layer include an acrylic adhesive, a rubber adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polymer. Amine-based adhesives, urethane-based adhesives, styrene-diene block copolymer-based adhesives, and the like. Among them, an acrylic adhesive or a silicone adhesive is preferred. In addition, the said adhesive can be used individually or in combination of 2 or more types.

As the acrylic pressure-sensitive adhesive contained in the second pressure-sensitive adhesive layer, for example, the pressure-sensitive adhesive described in the above item B-1 is used.

As the silicone-based adhesive contained in the second adhesive layer, any appropriate adhesive can be used. As the silicone-based adhesive, for example, a silicone-based adhesive using a silicone rubber or silicone resin containing an organic polysiloxane as a base polymer can be preferably used. As the base polymer constituting the silicone-based adhesive, a base polymer obtained by crosslinking the above-mentioned silicone rubber or silicone resin can be used. In addition, in this specification, the difference between "silicone rubber" and "silicone resin" is based on the material design and functionality of the "Technical Information Association Adhesive (Film / Tape)" First Edition September 30, 2009 222 ~ 228 pages ". That is, "silicone rubber" refers to a silicone having a linear structure composed of diorganosiloxane (D unit), and the silicone rubber has a viscosity of about 10,000 Pa · s, for example. A "silicone resin" refers to a silicone having a branched structure including triorganosilhemioxane (M unit) and silicate (Q unit).

The gel fraction of the second adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 99% by weight, and still more preferably 50% by weight to 99% by weight. If it is this range, the increase of the adhesive force after heating can be suppressed, and the laminated part A which is excellent in peelability can be comprised. The gel fraction was measured as follows.
<Method for measuring gel fraction>
A sample of about 0.1 g of the second adhesive layer was sampled and accurately weighed (the weight of the sample). The sample was wrapped in a mesh sheet (trade name "NTF-1122", manufactured by Nitto Denko Corporation), and then packed in about 50 ml. The toluene was immersed at room temperature for 1 week. Then, the solvent-insoluble component (the content of the mesh sheet) was taken out from toluene, and dried at 70 ° C for about 2 hours. The solvent-insoluble component (the weight after impregnation and drying) after drying was weighed, and the following formula was used: (a) Calculate the gel fraction (% by weight).
Gel fraction (% by weight) = [(Weight after dipping and drying) / (Weight of sample)] × 100 (a)

The base polymer constituting the adhesive B preferably has an OH group or a COOH group. The reason is that if such a base polymer is used, the above-mentioned gel fraction can be adjusted using a crosslinking agent.

C-2. Second substrate As the second substrate, for example, resin sheets, non-woven fabrics, paper, metal foil, woven fabrics, rubber sheets, foamed sheets, laminates of these (especially those containing resin sheets) Laminated body) and so on. A resin sheet is preferred. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene (PE). , Polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamine (aromatic polyamine), polyimide ( PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine-based resin, polyetheretherketone (PEEK), and the like. Among them, PET or PI is preferred.

The thickness of the second substrate is preferably 8 μm to 400 μm, more preferably 15 μm to 300 μm, and even more preferably 25 μm to 200 μm. Within this range, thermal degradation of the first adhesive layer can be significantly prevented.

The second substrate may be surface-treated. Examples of the surface treatment include the treatment described in the above item B-2. The surface treatment layer may be formed on a surface on the side of the second adhesive layer.

D. Manufacturing method of adhesive sheet
The adhesive sheet of the present invention can be produced by any appropriate method. In one embodiment, after forming the heat-peelable adhesive tape, the second base material is laminated on the second base material via the second adhesive layer on the opposite side of the first base material of the heat-peelable adhesive tape, By laminating the laminated portion A, the above-mentioned adhesive sheet can be manufactured.

The heat-peelable pressure-sensitive adhesive tape can be produced by any appropriate method. The heat-peeling type adhesive tape can be exemplified by a method in which the first substrate is directly coated with an adhesive A that includes a first adhesive layer (when a first adhesive layer including a thermally expandable microsphere is formed). Method further comprising a composition A for forming an adhesive layer containing thermally expandable microspheres); or transferring a coating layer formed by applying the composition A for forming an adhesive layer on any appropriate substrate to a first substrate Methods, etc. The composition A for forming an adhesive layer may contain any appropriate solvent. In the case where the first adhesive layer containing the thermally expandable microspheres is formed, after the adhesive coating layer is formed from the composition containing the adhesive A, the thermally expandable microspheres are scattered on the adhesive coating layer. Then, using a laminator or the like, the heat-expandable microspheres are embedded in the coating layer to form a first adhesive layer containing the heat-expandable microspheres.

The content ratio of the thermally expandable microspheres in the composition A for forming an adhesive layer is preferably 5 to 95% by weight, and more preferably 10 to 70% by weight relative to the weight of the solid content of the composition for forming an adhesive layer. % By weight, more preferably 10% by weight to 50% by weight.

The laminated portion A can be produced by any appropriate method. Regarding the above-mentioned laminated portion A, for example, a method of directly applying an adhesive layer-forming composition B including an adhesive B forming a second adhesive layer on a second substrate, or any appropriate method A method of transferring the coating layer formed by applying the adhesive layer-forming composition B on a substrate to a second substrate, and the like. The composition B for forming an adhesive layer may contain any appropriate solvent.

As a coating method of each of the above-mentioned compositions, any appropriate coating method can be adopted. For example, each layer can be formed by drying after coating. Examples of the coating method include coating methods using a multi-coater, a die coater, a gravure coater, and an applicator. Examples of the drying method include natural drying and heat drying. In the case of heating and drying, the heating temperature can be set to any appropriate temperature according to the characteristics of the substance to be dried.

E. Method for conveying thermal peeling type adhesive tape
The transport method of the heat-peelable pressure-sensitive adhesive tape of the present invention is the above-mentioned method of transporting the heat-peelable pressure-sensitive adhesive tape. The first base material side carries a heat-peelable pressure-sensitive adhesive tape with a build-up portion A. As described above, the build-up portion A includes the second adhesive layer and the second substrate. The lamination part A is arrange | positioned so that the 2nd base material may be laminated | stacked via the 2nd adhesive agent on the opposite side of the 1st base material of a heat release type adhesive tape from a 1st adhesive agent layer.

In one embodiment, the transfer method includes transferring a heat-peelable pressure-sensitive adhesive tape (substantially a heat-peelable pressure-sensitive adhesive tape with a build-up layer portion A) using a transfer roller. It is preferable that the heat-peeling type adhesive tape with the build-up part A is conveyed so that the build-up part A becomes a conveyance roller side. According to the conveying method of the present invention, by using the lamination section A to convey the heat-peeling type adhesive tape, the first adhesive layer can be protected from temperature rise due to the influence of friction with the conveying roller and the like. According to the present invention, by providing a build-up portion A20 laminated in a peelable manner, deterioration of the adhesive layer (that is, the first adhesive layer) of the heat-peeling type adhesive tape can be prevented, and it can be used as a heat-peeling type adhesive tape. It is made into a thickness suitable for practical use.
[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. In the examples, unless otherwise specified, "parts" and "%" are based on weight.

[Example 1]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: 95 parts by weight of acrylic acid: 5 parts by weight) and 3 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (thickness: 50 μm) as a second substrate so that the thickness became 5 μm after drying, and dried to form a second adhesive layer. The PET release film (thickness: 38 μm) was bonded to the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).

[Example 2]
Except that a polyimide film (thickness: 50 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (second substrate ( Thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).

[Example 3]
Except that a PET film (thickness: 25 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (thickness: 25) was obtained in the same manner as in Example 1. μm) / second adhesive layer (thickness: 5 μm) / separator).

[Example 4]
Except that a PET film (thickness: 100 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (thickness: 100) was obtained in the same manner as in Example 1. μm) / second adhesive layer (thickness: 5 μm) / separator).

[Example 5]
Except that the thickness of the second adhesive layer was set to 25 μm, a laminated portion A (second substrate (thickness: 50 μm)) / second adhesive layer (thickness: 25) was obtained in the same manner as in Example 1. μm) / separator).

[Example 6]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: hydroxyethyl acrylate (weight ratio) = 100: 4), and an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry, trade name "CORONATE L") 2 parts by weight, 0.05 parts by weight of a crosslinking accelerator (manufactured by Tosoh Corporation, trade name "Triethylenediamine (TEDA)") and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (50 μm) as a second substrate so that the thickness became 10 μm after drying, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 10 μm) / separator).

[Example 7]
100 parts by weight of an acrylic copolymer (butyl acrylate: acrylic acid (weight ratio) = 100: 5), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry, trade name "CORONATE L"), and epoxy-based 0.5 parts by weight of a cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD C") and toluene were mixed to prepare an adhesive solution. On the PET film (50 μm) as the second substrate, apply the above adhesive solution so that the thickness after drying becomes 50 μm and dry to form a second adhesive layer, and attach a PET release film (38 μm) Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 50 μm) / separator).

[Example 8]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight) and 5 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was coated on a PET film (50 μm) as a second substrate so that the thickness became 5 μm after drying, and dried to form a second adhesive layer. A PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).

[Example 9]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: 95 parts by weight of acrylic acid: 5 parts by weight) and 3 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (5 μm) as a second substrate so that the thickness after drying became 3 μm, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 5 μm) / second adhesive layer (thickness: 3 μm) / separator).

[Example 10]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight) and 0.6 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (50 μm) as a second substrate so that the thickness became 10 μm after drying, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 10 μm) / separator).

[Example 11]
Except that the thickness of the second adhesive layer was set to 50 μm, a laminated portion A (second substrate (thickness: 50 μm)) / second adhesive layer (thickness: 50) was obtained in the same manner as in Example 10. μm) / separator).

[Example 12]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight), and 6 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was coated on a PET film (50 μm) as a second substrate so that the thickness after drying became 3 μm, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 3 μm) / separator).

＜ Evaluation ＞
The laminated part A produced in the Example and the adhesive sheet containing the laminated part A and the heat-peeling type adhesive tape were evaluated for the following evaluation. The results are shown in Table 1.
Moreover, the adhesive sheet which consists only of a heat release type adhesive tape without the laminated part A was provided for the protective evaluation of (4) heat release type adhesive tape, and this was made into the result of the comparative example 1.
(1) Normal adhesion of the laminated part A (second substrate / second adhesive layer) Cut the laminated portion A (second substrate / second adhesive layer) produced in the example into a width: 20 mm 、 Length: 140 mm. After peeling the release film, adhere to the second adhesive layer according to JIS Z 0237 (2000) to form a polyethylene terephthalate film (brand name “Lumirror”). S-10 "manufactured by Toray; thickness: 50 μm, width: 20 mm) (Specifically, a 2 kg roller is reciprocated once in an environment of temperature: 23 ± 2 ° C and humidity: 65 ± 5% RH Pressure-bonding and bonding) to prepare a sample for evaluation. This sample for evaluation was attached to a tensile tester (made by Shimadzu Corporation, trade name "Shimadzu Autograph AG-120kN") with a thermostatic bath set at 23 ° C, and left for 30 minutes. After standing, the load at the time of peeling of the adherend at 23 ° C under the conditions of peeling angle: 180 °, peeling speed (stretching speed): 300 mm / min was measured, and the weight at this time was determined. Concave-convex average load (average of concavities and convexities of loads other than the peak at the beginning of the measurement), and the average uneven-convex load was used as the adhesion force (N / 20 mm width) of the laminated portion A.

(2) The adhesive force after heating of the laminated portion A (second substrate / second adhesive layer) was prepared in the same manner as in (1) above.
The sample for evaluation was heated at 100 ° C for 30 minutes, and then left to stand in an environment of 23 ° C for 30 minutes. Thereafter, the sample for evaluation was attached to a tensile tester (trade name "Shimadzu Autograph AG-120kN", manufactured by Shimadzu Corporation) with a thermostat set at 23 ° C, and left for 30 minutes. After standing, the load at the time of peeling of the adherend at 23 ° C under the conditions of peeling angle: 180 °, peeling speed (stretching speed): 300 mm / min was measured, and the weight at this time was determined. Concave-convex average load (average of concavities and convexities of loads other than the peak at the beginning of the measurement), and the average uneven-convex load was used as the adhesion force (N / 20 mm width) of the laminated portion A.
In addition, based on the measured values, the peelability of the laminated portion A was evaluated according to the following criteria. In addition, when the peelability here is actually used, it may be equivalent to supplying a pressure-sensitive adhesive sheet composed of a heat-peeling type adhesive tape and the laminated part A to a roll-to-roll process, and the temperature may be affected by the friction with the transfer roller. Peelability after rising.
: Adhesion after heating is 5.0 N / 20 mm or less Δ: Adhesion after heating exceeds 5.0 N / 20 mm

(3) Take a sample of the gel fraction of the second adhesive layer to sample about 0.1 g of the adhesive layer that constitutes layer A and weigh it accurately (weight of the sample). Use a mesh sheet (trade name "NTF-1122") for this sample. ", Manufactured by Nitto Denko Co., Ltd.) After wrapping, immerse in about 50 ml of toluene at room temperature for 1 week. Then, the solvent-insoluble component (the content of the mesh sheet) was taken out from toluene, and dried at 70 ° C for about 2 hours. The solvent-insoluble component (the weight after impregnation and drying) after drying was weighed, and the following formula was used: (a) Calculate the gel fraction (% by weight).
Gel fraction (% by weight) = [(Weight after dipping and drying) / (Weight of sample)] × 100 (a)

(4) Evaluation of the protective property of the heat-peelable adhesive tape Using a hand roller, the laminated part A produced in the example was bonded to the first substrate (PET film, thickness: 50 μm), the intermediate layer, and the first adhesive layer. The first base material surface of the heat-peelable pressure-sensitive adhesive tape composed of an adhesive layer was obtained as an adhesive sheet for evaluation (first adhesive layer (thermal peelability) / intermediate layer / first substrate / second adhesive layer / second base). material). The heat-peelable pressure-sensitive adhesive tape system is produced by the following method.
30 parts by weight of 100% by weight of an acrylic copolymer (butyl acrylate: hydroxyethyl acrylate = 100 parts by weight: 3 parts by weight) is formulated with a terpene phenol-based adhesion-imparting resin (trade name "YS Polystar T80", manufactured by Yasuhara Chemical Co., Ltd.) Parts, 1 part by weight of isocyanate-based cross-linking agent (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry, Inc.), toluene was added thereto, and they were mixed uniformly to prepare an adhesive solution, which was applied to a PET substrate (first substrate, thickness: 50) μm) The above-mentioned adhesive solution was applied so that the thickness after drying became 20 μm to form an intermediate layer.
Furthermore, 1 part by weight of an isocyanate-based crosslinking agent (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry) and a foaming agent (heat-expandable microsphere; trade name "Matsumoto Microsphere") were uniformly mixed with 100 parts by weight of the copolymer. F-30D ", manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd.) and 50 parts by weight of toluene, and dissolving them, and the obtained coating liquid was applied to a PET substrate release film (38 μm thickness after drying) μm) to form a first adhesive layer. The pressure-sensitive adhesive layer was transferred onto the intermediate layer to obtain the heat-peelable pressure-sensitive adhesive tape.
The probe adhesive force of the first adhesive layer of the sample for evaluation was measured under the following conditions, and the value was set to C ₀ . The self-evaluation sample was heated on the back surface (second substrate) side under the following conditions, and the probe adhesion C after heating was measured. The probe adhesive force residual ratio was calculated by the formula (C / C ₀ ) × 100.
When the thermally expandable microspheres start to foam due to the influence of the heat from the back surface, the value of the probe adhesive force becomes smaller, and the residual rate of the probe adhesive force becomes smaller. Therefore, based on the magnitude of the probe adhesion residual rate, the protective properties of the heat-peelable adhesive tape in the adhesive sheet were evaluated according to the following criteria.
: Probe adhesion residual rate is 80% or more Δ: Probe adhesion residual rate is 70% or more and less than 80%
×: Residual adhesion of probe is less than 70%
In the comparative example, the heat-peelable pressure-sensitive adhesive tape produced as described above was directly used as an evaluation tape, and was used for the above-mentioned evaluation.
・ Heating method: Place the second substrate (the first substrate in the comparative example) on the heating plate side and place it on a heating plate heated to 90 ° C, and then contact the tape evenly from above the adhesive tape for evaluation and heat it. Place the weight of the glass (140 mm × 140 mm × 10 mm) in the form of a plate. This state was maintained for 20 seconds, and the adhesive tape for evaluation was heated.
-Probe adhesion measurement method The adhesion tester TAC-II (manufactured by RHESCA) was used to evaluate the probe adhesion under the following conditions. The peak load (gf) applied at the time of extraction was taken as the value of the probe adhesion.
・ Metal probe diameter 10 mm
・ Pressing speed of probe: 30 mm / min ・ Load capacity: 50gf
・ Press-in time 0.5 seconds ・ Pull-out speed 30 mm / min

(5) Evaluation of stability of laminated layer A In the same manner as in (4) above, an adhesive tape for evaluation was produced.
The adhesive tape for evaluation was cut into a size of 20 mm × 100 mm. The short strip-shaped adhesive tape for evaluation was bent in half with respect to the longitudinal direction so that the side of the laminated portion A was inward, and then stretched to the original state.
The crease portion was visually observed and evaluated according to the following criteria.
: No bulge was confirmed between the first base material surface of the heat-peelable pressure-sensitive adhesive tape and the second adhesive layer of the laminated portion A. A bulge was confirmed between the first base material surface and the second adhesive layer, but Practically tolerable ×: A bulge of a degree not practically acceptable was confirmed between the first substrate surface and the second adhesive layer

[Table 1]

10‧‧‧Heat release type adhesive tape

11‧‧‧The first adhesive layer

12‧‧‧ the first substrate

20‧‧‧Laminated part A

21‧‧‧Second adhesive layer

22‧‧‧ 2nd substrate

100‧‧‧ Adhesive sheet

FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention.

Claims (10)

An adhesive sheet includes: a first adhesive layer, a first substrate, a second adhesive layer, and a second substrate in this order, The first adhesive layer and the first substrate constitute a heat-peelable adhesive tape, The second adhesive layer and the second base material constitute a laminated portion A, The laminated portion A is disposed so as to be peelable from the heat-peelable pressure-sensitive adhesive tape. For example, the adhesive sheet of claim 2, wherein the thickness of the laminated portion A is 10 μm or more. For example, the adhesive sheet of claim 1 or 2, wherein the thickness of the first adhesive layer is 1 μm to 30 μm. For example, the adhesive sheet of claim 1 or 2, wherein the elastic modulus of the first adhesive layer at 25 ° C obtained by the nanoindentation method does not reach 100 MPa. For example, the adhesive sheet of claim 1 or 2, wherein the gel fraction of the second adhesive layer is 20% to 100% by weight. For example, the adhesive sheet of claim 1 or 2, wherein the thickness of the second adhesive layer is 1 μm to 100 μm. For example, the adhesive sheet of claim 1 or 2, wherein the thickness of the second substrate is 8 μm to 400 μm. For example, the adhesive sheet of claim 1 or 2, wherein the adhesive force A2 on the polyethylene terephthalate film after heating the laminated part A at 100 ° C for 30 minutes with respect to the laminated part A on polyterephthalic acid The normal state adhesive force A1 of the ethylene glycol film is 10 times or less. For example, the adhesive sheet of claim 1 or 2, wherein the normal adhesive force A1 of the laminated portion A to the polyethylene terephthalate film is 0.05 N / 20 mm to 5 N / 20 mm. A method for transferring a heat-peeling type adhesive tape, which is a method for transferring a heat-peeling type adhesive tape having a first substrate and a first adhesive layer, and The conveying method includes laminating the laminated portion A on the first substrate side, and conveying the heat-peelable adhesive tape with the laminated portion A.