TWI714815B - Articles, article manufacturing methods and void filling methods - Google Patents

Abstract

The problem to be solved by the present invention is to provide an adhesive tape that has excellent adhesion before heating, can be expanded by heating, and can still exhibit excellent adhesion after heating and expansion. The present invention is an adhesive tape, which is used to fill the voids of the adherend (C1) or the gap between the adherend (C1) and the adherend (C2), and is characterized by: the adhesive The tape has a thermoplastic heat-expandable adhesive layer (A), the expansion rate of the thermoplastic heat-expandable adhesive layer (A) in the thickness direction [the thickness of the thermoplastic heat-expandable adhesive layer (A1) after heating/before heating The thickness of the thermoplastic heat-expandable adhesive layer (A)]×100% is 150% or more.

Description

Articles, article manufacturing methods and void filling methods

The present invention relates to an adhesive tape having a structure capable of swelling in the thickness direction by giving stimulation such as heating at a low temperature and a short time.

Adhesive tapes are generally ideal for fixing the flat part or curved part of one adherend to the other. It has been widely used in the manufacture of various products such as automotive components and electrical equipment. occasion.

On the other hand, when we look forward to the ever-expanding use of adhesive tapes, there is a need for the aforementioned adhesive tapes to be ideally used, for example, to fix another adherend in a gap provided by an adherend. Specifically, as a motor mounted in a hybrid electric vehicle, etc., it is generally known that there is a structure in which a magnet is embedded in a predetermined position (a gap) of the core (rotor core), and it is studied to fix the magnet to The aforementioned adhesive tape is used in the voids of the aforementioned core portion.

Regarding the adhesive tape that can be used for the aforementioned purposes, for example, a thermosetting thermally expandable adhesive sheet is known, which has a base material and a first adhesive layer, the base material has a first surface and is located on the first surface The second surface on the opposite side has a communicating port. The first adhesive layer is formed on the first surface of the substrate and contains thermosetting thermal expansion. Expandable epoxy adhesive, the thermosetting heat-expandable epoxy adhesive will pass through the communication port of the substrate when heated to form a second adhesive layer on the second surface of the substrate (for example, refer to Patent Document 1.).

However, the aforementioned thermosetting adhesive tape does not have sufficient adhesive force in the state before heating, so it may be difficult to temporarily attach (temporarily adhere) the thermosetting adhesive tape to the predetermined position of the adherend before heating. In this case, even if it can be temporarily attached, the aforementioned thermosetting adhesive tape will deviate from the adherend.

[Prior technical literature]

〔Patent Literature〕

[Patent Document 1] Japanese Patent Application Publication No. 2010-023559

The problem to be solved by the present invention is to provide an adhesive tape that has excellent adhesion before heating, can be expanded by heating, and can still exhibit excellent adhesion after heating and expansion.

The inventors of the present case solved the above problem with the following adhesive tape: an adhesive tape used in the gap between the adherend (C1) or the adherend (C1) and the adherend (C2) The use of filling the gaps is characterized in that the adhesive tape has a thermoplastic heat-expandable adhesive layer (A), and the expansion rate in the thickness direction of the thermoplastic heat-expandable adhesive layer (A) (thermoplastic heat-expandable adhesive after heating) The thickness of the adhesive layer (A1)/the thickness of the thermoplastic heat-expandable adhesive layer (A) before heating]×100% is 150% or more.

The adhesive tape of the present invention has excellent adhesion, can be attached to the correct position of the adherend even before heating, and will not cause the sticking position of the adhesive tape to shift after temporary attachment, so it can The gap between the adherend and the gap between two or more adherends are fully filled or bonded.

1: Aluminum plate (C1)

2: Aluminum plate (C2)

3: Spacer

4: Adhesive tape

5: The gap between the adhesive tape and the aluminum plate (C2)

[Figure 1] is a conceptual diagram showing the method of measuring shear adhesion.

The adhesive tape of the present invention: an adhesive tape used to fill the voids of the adherend (C1) or the gap between the adherend (C1) and the adherend (C2), and its characteristics It is: the adhesive tape has a thermoplastic heat-expandable adhesive layer (A), the expansion rate in the thickness direction of the thermoplastic heat-expandable adhesive layer (A) [the thickness of the thermoplastic heat-expandable adhesive layer (A1) after heating /The thickness of the thermoplastic thermally expandable adhesive layer (A) before heating]×100% is 150% or more.

The adhesive tape of the present invention uses at least one having the aforementioned thermoplastic thermally expandable adhesive layer (A).

Examples of the adhesive tape include adhesive tapes composed of a single layer or two or more layers of the thermoplastic heat-expandable adhesive layer (A), and the thermoplastic heat-expandable adhesive layer (A) and other expandable adhesives. Adhesive layer (such as light-expandable adhesive layer, thermosetting expansive adhesive layer) composed of adhesive tape, from the front The thermoplastic heat-expandable adhesive layer (A) and an adhesive layer that is difficult to expand (for example, the adhesive layer (B), etc. described later) are adhesive tapes.

Among them, if an adhesive tape composed of the thermoplastic heat-expandable adhesive layer (A) and other adhesive layers is used as the adhesive tape, the swelling of the adhesive tape will have the adherend (C1) It is preferable to fill the gap or the gap between the adherend (C1) and the adherend (C2) and firmly bond them.

The adhesive tape composed of the aforementioned thermoplastic heat-expandable adhesive layer (A) and other adhesive layers, specifically, it is suitable to use at least one side of the aforementioned thermoplastic heat-expandable adhesive layer (A) that has the following adhesive Adhesive tape of agent layer (B). For the aforementioned adhesive tape, the thermoplastic heat-expandable adhesive layer (A) is attached to the adherend in advance before the expansion, and the expanded thermoplastic heat-expandable adhesive layer (A1) and the aforementioned The viewpoint of the excellent adhesion of the adherend is preferable.

(Thermoplastic heat-expandable adhesive layer (A))

The said thermoplastic heat-expandable adhesive layer (A) is a layer which can expand by heating, for example. Regarding the aforementioned thermoplastic heat-expandable adhesive layer (A), the expansion rate in the thickness direction of the thermoplastic heat-expandable adhesive layer (A) is used [the thermoplastic heat-expandable adhesive layer (A) after the aforementioned placement after heating The thickness/thickness of the thermoplastic heat-expandable adhesive layer (A) before placement]×100% is 150% or more. The aforementioned expansion ratio is preferably 200% or more, more preferably 250% to 1000%. If it is such an adhesive tape, even if the gap between the adherend (C1) or the height (thickness) of the gap between the adherend (C1) and the adherend (C2) is large, it can still be used The adhesive tape is expanded, and another adherend is ideally fixed in the gap or the gap is filled with the adhesive tape. Moreover, in the case of the aforementioned adhesive tape, even if the surface of the adherend is a rough surface, another adherend can be ideally fixed to the rough surface.

In addition, the aforementioned expansion ratio refers to the thermoplastic heat-expandable adhesive formed by the expansion of the thermoplastic heat-expandable adhesive layer (A) when the aforementioned adhesive tape is placed at a temperature of 50°C to 150°C for 30 minutes. The ratio of the thickness of the layer (A1) to the thickness of the thermoplastic heat-expandable adhesive layer (A) before placing (before expansion), but the temperature of 60℃~145℃ is better, and the temperature of 70℃~140℃ The temperature is better.

As the aforementioned thermoplastic heat-expandable adhesive layer (A), it is preferable to use peeling at a speed of 300mm/min in a 180 degree direction from the viewpoint of imparting adhesiveness to the extent that it can be temporarily attached to the adherend even before heating. When the adhesive force is 0.5N/20mm or more, it is better to use 1N/20mm or more, and it is better to use 2N/20mm or more. If it is 3N/20mm or more, it will prevent the aforementioned adhesive tape from peeling off the adherend. The point of view of position shift is even better.

The thickness of the aforementioned thermoplastic heat-expandable adhesive layer (A) before expansion is preferably in the range of 10 μm to 250 μm, more preferably in the range of 20 μm to 150 μm, and if it is in the range of 30 μm to 100 μm, it can be applied even before heating. It is preferable from the viewpoint of adhesion to the extent that it is temporarily attached to the adherend and prevents the aforementioned adhesive tape from peeling off the adherend and position shift.

On the other hand, the thickness of the thermoplastic heat-expandable adhesive layer (A1) formed by the expansion of the aforementioned thermoplastic heat-expandable adhesive layer (A) is preferably in the range of 20 μm to 2500 μm, and in the range of 40 μm to 1500 μm. The viewpoint of more excellent adhesive force is preferable. Furthermore, the aforementioned thermoplastic thermally expandable adhesive layer (A1) is preferably one having a porous structure.

In addition, as the adhesive tape, it is preferable to use the thickness of the thermoplastic heat-expandable adhesive layer (A) with respect to the total thickness of the adhesive tape being 10% or more. If it is 30% or more, it is easy to stick another The body is ideally fixed in the aforementioned void, or it is easier to fill the aforementioned void with the aforementioned adhesive tape, which is more preferable.

As the aforementioned thermoplastic heat-expandable adhesive layer (A), use the pressure that has the adhesive force to the extent that it can be pre-bonded to the adherend and can expand with the aforementioned thermoplastic heat-expandable adhesive layer (A) Filling and bonding the gap between the adherend (C1) or the gap between the adherend (C1) and the adherend (C2).

The aforementioned thermoplastic heat-expandable adhesive layer (A) can be manufactured by applying the adhesive composition (a) described later on, for example, a mold release pad, an adhesive tape support, and drying.

The adhesive composition (a) containing a thermoplastic resin can be used to form the aforementioned thermoplastic thermally expandable adhesive layer (A). The content of the aforementioned thermoplastic resin relative to the total solid content of the adhesive composition (a) is preferably 50% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more.

As for the aforementioned thermoplastic resin, one that can be easily expanded by heating can be used.

As the aforementioned thermoplastic resin, the storage elastic modulus G ₂₃ measured by dynamic viscoelastic spectrum at 1 Hz and 23°C is preferably in the range of 1.0×10 ³ to 5.0×10 ⁷ Pa, and it is suitable to be used at 1 Hz and 70° C. The storage elastic modulus G ₇₀ measured by the viscoelastic spectrum is in the range of 1.0×10 ² to 1.0×10 ⁷ Pa, and the storage elastic modulus G ₁₂₀ measured by the dynamic viscoelastic spectrum at 1 Hz and 120°C is 1.0×10 ^In the range of ² to 1.0×10 ⁶ Pa, it is possible to obtain the viewpoint that the adhesive tape can prevent the adhesive tape from peeling off and position shift from the adherend even before heating, and can expand to the extent that the gap can be sufficiently filled. It is especially good.

Regarding the adhesive tape in the state before the thermoplastic heat-expandable adhesive layer (A) is expanded, it is considered that the adhesive tape can be prevented from peeling off the adherend and positional shift even before heating, and will prevent the expansion after the From the viewpoint of shrinkage under normal temperature environment, the storage elastic modulus G ₂₃ measured by dynamic viscoelastic spectrum at 1Hz and 23℃ can be used, preferably 1.0×10 ³ ~5.0×10 ⁷ Pa, more preferably 5.0×10 ³ ~ 1.0×10 ⁷ Pa, particularly preferably a thermoplastic resin of 5.0×10 ³ ~5.0×10 ⁶ Pa.

In addition, for the aforementioned thermoplastic resin, a storage elastic modulus G ₂₃ measured at 1 Hz and 23°C with a dynamic viscoelastic spectrum in the above range is used, and a dynamic viscoelastic spectrum at 1 Hz in the range of 70°C to 120°C is used If the measured storage elastic modulus is in the range of 1.0×10 ² Pa to 1.0×10 ⁷ Pa, the viewpoint of suppressing the expansion of the adhesive tape in the plane direction (travel direction, width direction) and expanding it in the thickness direction is relatively good.

As the aforementioned thermoplastic resin, the storage elastic modulus G ₇₀ measured by dynamic viscoelastic spectrum at 1 Hz and 70°C is preferably 1.0×10 ² to 1.0×10 ⁷ Pa, more preferably 5.0×10 ² to 5.0×10 ⁶ Pa, particularly preferably 5.0×10 ² to 1.0×10 ⁶ Pa.

In addition, as the aforementioned thermoplastic resin, the storage elastic modulus G ₇₀ measured by dynamic viscoelastic spectrum at 1 Hz and 70° C. is preferably 1.0×10 ² to 1.0×10 ⁷ Pa, more preferably 5.0×10 ² to 5.0 ×10 ⁶ Pa, particularly preferably 5.0×10 ² to 1.0×10 ⁶ Pa.

In addition, the storage elastic modulus G _{120 of the} aforementioned thermoplastic resin measured by dynamic viscoelastic spectrum at 1 Hz and 120°C is preferably 1.0×10 ² to 1.0×10 ⁶ Pa, more preferably 5.0×10 ² to 5.0×10 ⁶ Pa, more preferably 5.0×10 ² to 2.0×10 ⁵ Pa.

The storage elastic modulus G _{120 of the} thermoplastic resin is preferably smaller than the storage elastic modulus G ₇₀ , and the storage elastic modulus G _{70 is} preferably smaller than the storage elastic modulus G ₂₃ .

In addition, the aforementioned storage elastic modulus G ₂₃ , G ₇₀ and G ₁₂₀ were measured by using a commercially available viscoelastic tester and the method described in the following examples. As for the test piece measured above, the one obtained by heating the thermoplastic resin (without expansion agent) contained in the thermoplastic heat-expandable adhesive layer (A), coating it on the release pad, and then cooling it Test piece with thickness 2mm.

For the aforementioned thermoplastic resin, it is preferable to use, for example, one that has excellent adhesive force before expansion, will soften at the expansion start temperature of the expansion agent, and the expansion agent is easy to expand, and can still exhibit excellent adhesion even after expansion.

Examples of the aforementioned thermoplastic resin include: urethane-based resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); polyvinyl chloride (PVC), vinyl chloride- Vinyl chloride resins such as vinyl acetate copolymer resins; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; polyterephthalate Polyester resins such as ethylene formate (PET), polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; nylon (registered Trademark) and other polyamide resins; polystyrene (PS), imine modified polystyrene, acrylonitrile. Butadiene. Styrene (ABS) resin, imine modified ABS resin, styrene. Acrylonitrile copolymer (SAN) resin, acrylonitrile. Ethylene-propylene-diene. Polystyrene resins such as styrene (AES) resin, olefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, and cycloolefin resin; cellulose resins such as nitrocellulose and cellulose acetate; poly Silicone-based resins; thermoplastic resins such as fluorine-based resins, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based Thermoplastic elastomers such as thermoplastic elastomers.

Among these, as thermoplastic resins, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, ester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and amide-based thermoplastic elastomers are particularly suitable. Thermoplastic elastomer or acrylic resin, etc., particularly preferably styrene-based thermoplastic elastomer or acrylic resin.

Examples of styrene-based thermoplastic elastomers include styrene-based AB diblock copolymers such as styrene-ethylene-butene copolymer (SEB); styrene-butadiene-styrene copolymer (SBS), SBS Hydride (styrene-ethylene-butylene-styrene copolymer (SEBS)), styrene-isoprene-styrene copolymer (SIS), SIS hydride (styrene-ethylene-propylene-benzene Styrenic ABA triblock copolymers such as ethylene copolymer (SEPS) and styrene-isobutylene-styrene copolymer (SIBS); styrene-butadiene-styrene-butadiene (SBSB) and other benzene Ethylene ABAB tetrablock copolymer; styrene-butadiene-styrene-butadiene-styrene (SBSBS) and other styrene ABABA pentablock copolymers; with AB repeating units above these Styrenic multi-block copolymers; hydrogenated products obtained by hydrogenating the ethylenic double bonds of styrene random copolymers such as styrene-butadiene rubber (SBR); etc. Commercially available styrene-based thermoplastic elastomers can also be used.

The aforementioned acrylic resin can be obtained by polymerizing a monomer containing alkyl (meth)acrylate, for example.

For the aforementioned alkyl (meth)acrylates, (meth)acrylates having an alkyl group with 4 to 12 carbon atoms are preferably used, specifically, butyl (meth)acrylate and isooctyl (meth)acrylate are used. Ester, 2-ethylhexyl (meth)acrylate, etc. are preferred, and butyl acrylate and 2-ethylhexyl acrylate are more preferably used alone or in combination.

Moreover, as the aforementioned monomer, in addition to the aforementioned, acrylonitrile, (meth)acrylic acid, maleic anhydride, acrylamide, itaconic acid, styrene, vinyl acetate, etc. can be used.

The aforementioned adhesive composition (a) may contain a thermosetting resin. As the thermosetting resin, urethane resin, phenol resin, unsaturated polyester resin, epoxy resin, acrylic resin, etc. can be used. Among them, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydantoin type epoxy resin, biphenyl type epoxy resin, alicyclic ring Oxygen resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type Epoxy resin, dicyclopentadiene/phenol epoxy resin, cycloaliphatic amine epoxy resin, aliphatic amine epoxy resin, and CTBN modification (carboxyl-terminated butadienenitrile modification), The halogen-modified epoxy resin or the like is used alone or in combination of two or more kinds.

The content of the aforementioned thermosetting resin relative to the total solid content of the adhesive composition (a) is preferably 50% by mass or less, more preferably 25% by mass or less, and still more preferably 10% by mass or less.

啉基-1,2,3,4-噻三唑等三唑化合物、N,N’-二亞硝基對苯二甲醯胺等N-亞硝基化合物。 The aforementioned adhesive composition (a) may also contain a swelling agent. As the expansion agent, it is preferable to use the one that can form a porous structure with respect to the expanded thermoplastic thermally expandable adhesive layer (A1), for example, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, ammonium borohydride, azide compound can be used Inorganic compounds such as trichlorofluoromethane, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as p-toluenesulfonyl hydrazine, semicarbazide compounds such as p-toluenesulfonyl semicarbazide, 5-

Triazole compounds such as linyl-1,2,3,4-thiatriazole, and N-nitroso compounds such as N,N'-dinitroso-p-phthalamide.

In addition, the aforementioned expansion agent is preferably a thermal expansion agent that expands due to heat. For example, expandable capsules such as heat-expandable capsules obtained by microencapsulating a hydrocarbon solvent can be used. The aforementioned thermal expansion agent is preferably one that can generate gas and expand at a temperature around the softening point of the aforementioned thermoplastic resin. The expansion start temperature of the thermal expansion agent is preferably 50°C or higher, more preferably 60°C or higher. When it is 70°C or higher, the storage stability is excellent, and the adhesive tape can be sufficiently expanded without damaging the low-heat-resistant quilt. Adhesive body can obtain excellent adhesion after expansion, so it is better.

Using the aforementioned heat-expandable capsule obtained by microencapsulating a hydrocarbon-based solvent as the aforementioned expansion agent can prevent the deterioration of the thermoplastic heat-expandable adhesive layer (A) caused by heat, etc., for example. For better. The aforementioned expansion agent can be used alone or in combination of two or more kinds.

Examples of commercially available products of the thermally expandable capsule include Expancel (manufactured by Fillite Co., Ltd.), Matsumoto Microsphere (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd.), and Microsphere (manufactured by Kureha Co., Ltd.).

Use Matsumoto Microsphere F-30, F-36, F-36D, F-36LV, F-48, F-48D, F-50, FN-80GS, F-65, Japan Fillite ( Stock) Expancel 053-40, 007-40, 031-40 manufactured by the company as the aforementioned heat-expandable capsules will expand before and after the softening temperature of the thermoplastic resin, so the adhesive tape will be prevented from expanding in the plane direction (travel direction, width direction) , And can expand toward its thickness more effectively, so it is better.

The thermally expandable capsules should preferably use those whose volume after expansion is 8 to 60 times the volume (volume expansion rate) of the aforementioned capsule before expansion.

The usage amount of the aforementioned expansion agent is preferably the usage amount of the aforementioned heat-expandable capsule, which is preferably in the range of 0.3 to 30 parts by mass relative to 100 parts by mass of the solid content in all the components of the layer (A), which is 1 The range of parts by mass to 20 parts by mass is more preferable, and the range of 3 to 17 parts by mass is even more preferable. When it is in the range of 5 parts by mass to 15 parts by mass, it can expand sufficiently to fill the voids of the adherend, etc. To the extent, and will get better adhesion, so it is better.

As the aforementioned adhesive composition (a), in addition to the aforementioned substances, if necessary, an adhesive agent, a crosslinking agent, a hardening agent, a hardening accelerator, etc. can be used.

(Adhesive layer (B))

In addition, the adhesive tape of the present invention preferably has an adhesive layer (B) as described above.

The adhesive layer (B) constituting the aforementioned adhesive tape can be formed using an adhesive composition (b) capable of forming a layer with adhesiveness or adhesion.

The aforementioned adhesive layer (B) can use the expansion rate in the thickness direction of the aforementioned adhesive layer (B) [the thickness of the aforementioned adhesive layer (B) after heating/the aforementioned adhesive layer before placement (B) Thickness]×100% is 120% or less. The expansion rate of the aforementioned adhesive layer (B) is preferably 115% or less, more preferably 110% or less. If it is such an adhesive tape, even after the aforementioned thermoplastic heat-expandable adhesive layer (A) expands, it can still maintain an excellent adhesive force to the adherend. In addition, the expansion rate of the adhesive layer (B) refers to the thickness of the adhesive layer after placing the adhesive tape in an environment of 100°C for 30 minutes relative to the thickness of the adhesive before placing The ratio of the thickness of layer (B).

The thickness of the aforementioned adhesive layer (B) is preferably in the range of 1 μm to 150 μm, and if it is in the range of 5 μm to 100 μm, the thermoplastic heat-expandable adhesive layer (A) that constitutes the aforementioned adhesive tape can expand, and the adherend ( C1) Fill the gap between the adherend (C1) and the adherend (C2), and the adhesive layer (B) is applied to the adherend (C2). Adhesion is better.

The aforementioned adhesive layer (B) preferably has a low expansion rate as described above, and therefore, it is preferable that the expansion agent, which has been listed as what can be used when forming the aforementioned thermoplastic heat-expandable adhesive layer (A) is formed, is not substantially contained.

As for the aforementioned adhesive (B), it is desirable to use an adhesive composition (b) that contains resins such as thermosetting resins and thermoplastic resins, and contains little or no expansion agent.

Regarding the resin that can be used for the aforementioned adhesive composition (b), conventionally known resins can be selected and used. Among them, considering the viewpoint of improving the production efficiency of the adhesive tape of the present invention, the aforementioned resin is preferably used, for example, and the adhesive composition (a) that can be used for the formation of the aforementioned thermoplastic heat-expandable adhesive layer (A). The thermoplastic resin contained is the same.

As the aforementioned adhesive composition (b), for example, those containing resins such as the aforementioned thermoplastic resins, and if necessary, adhesion-imparting resins, crosslinking agents, other additives, and the like can be used.

Regarding the aforementioned adhesion-imparting resin, for the purpose of adjusting the strong adhesion of the adhesive layer (B), for example, rosin-based adhesion-imparting resin, polymerized rosin-based adhesion-imparting resin, polymerized rosin ester-based adhesion-imparting resin, rosin can be used Phenol-based adhesion imparting resin, stabilized rosin ester-based adhesion imparting resin, disproportionated rosin ester-based adhesion imparting resin, terpene-based adhesion imparting resin, terpene phenol-based adhesion imparting resin, petroleum resin-based adhesion imparting resin, etc.

唑啉系交聯劑、碳二亞胺系交聯劑、矽烷系交聯劑、環氧丙基(烷氧基)環氧矽烷系交聯劑等。 With regard to the aforementioned crosslinking agent, for the purpose of enhancing the cohesive force of the adhesive layer (B), well-known isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and polyvalent metals can be used Salt-based cross-linking agents, metal chelate-based cross-linking agents, ketones. Hydrazine-based crosslinking agent,

Oxazoline-based cross-linking agents, carbodiimide-based cross-linking agents, silane-based cross-linking agents, epoxypropyl (alkoxy) siloxane-based cross-linking agents, etc.

Regarding the aforementioned additives, if necessary, within a range that does not hinder the desired effect of the present invention, alkali (ammonia water, etc.), acid, foaming agent, plasticizer, softener, antioxidant, glass for adjusting pH , Plastic fibers, balloons, beads, metal powders, fillers, pigments, dyes and other colorants, pH adjusters, film formation aids, leveling agents, tackifiers, water repellents, and anti Well-known things such as foaming agents.

Regarding the aforementioned adhesive composition (b), a solvent can be used from the viewpoint of maintaining good coating workability. As the aforementioned solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, hexane, etc. can be used. In addition, when an aqueous adhesive composition is used as the adhesive composition (b), water or an aqueous solvent mainly composed of water can be used as the solvent.

The adhesive tape of the present invention can be manufactured, for example, through the following steps: step [I], the aforementioned adhesive composition (a) is coated on a release pad and dried to form a thermoplastic heat-expandable adhesive layer (A ).

Among the adhesive tapes of the present invention, the adhesive tape composed of the aforementioned thermoplastic thermally expandable adhesive layer (A) and the aforementioned adhesive layer (B) can be manufactured through the following steps: the aforementioned step [I]; step [II] , Different from the aforementioned step [I], in addition, the aforementioned adhesive composition (b) is coated on the release pad and dried, etc. to form the adhesive layer (B); and step [III], the aforementioned The adhesive layer (B) is transferred to one side of the aforementioned thermoplastic heat-expandable adhesive layer (A), and the adhesive layer (B) is crimped.

In addition, it is preferable that the thermoplastic heat-expandable adhesive layer (A) does not substantially swell in the process of manufacturing the adhesive tape.

In addition, the adhesive tape of the present invention can be used if necessary, with a non-woven fabric layer or a resin film layer or a layer (Z) made of metal between the aforementioned thermoplastic thermally expandable adhesive layer (A) and the adhesive layer (B). By. Since such an adhesive tape has good rigidity, it is excellent in sticking workability.

The aforementioned layer (Z), for example, when it is a non-woven fabric, it is suitable for the material to be composed of pulp, rayon, manila hemp, acrylonitrile, nylon, polyester, etc. In order to meet the tensile strength of the non-woven fabric, it can also be used in papermaking if necessary. Steps: One-step impregnation treatment of adding polyamide and coating after drying, two-step impregnation treatment using viscose fiber (viscose) and thermoplastic resin as a binder, etc. The resin film layer includes a resin film layer formed using plastic films such as polyester film, polyethylene film, polypropylene film, polyvinyl chloride film, polyimide film, etc.; the layer made of metal includes aluminum, Metal layers such as copper.

The aforementioned layer (Z) preferably has a thickness of 1 μm to 200 μm.

The adhesive tape with the aforementioned layer (Z), for example, can be manufactured through the following steps: step [I], the aforementioned adhesive composition (a) is coated on a release pad and dried to form a thermoplastic thermally expandable adhesive Agent layer (A); step [II], which is different from the aforementioned step [I], in addition, the aforementioned adhesive composition (b) is applied to the release pad and dried, etc. to form the adhesive layer (B ); Step [IV], laminating the aforementioned layer (Z) on one side of the aforementioned thermoplastic thermally expandable adhesive layer (A); and step [V], transferring the aforementioned adhesive on the surface composed of the aforementioned layer (Z) The adhesive layer (B) is crimped.

The adhesive tape of the present invention obtained by the above method, etc., can be expanded by heating and has excellent adhesion, so it can be ideally used for the adherend (C1) by the expansion of the adhesive tape of the present invention The manufacturing occasions of the article made by filling or bonding the gap between the adherend (C1) and the adherend (C2).

The manufacturing method of the aforementioned article can be, for example, a manufacturing method of the article, which includes the following steps: step [1], attaching the thermoplastic heat-expandable adhesive layer (A) or adhesive layer (B) of the aforementioned adhesive tape to The part (c1-1) constituting the adherend (C1); step [2], heating the aforementioned thermoplastic heat-expandable adhesive layer (A); step [3], bonding the aforementioned thermoplastic heat-expandable adhesive by the aforementioned heating The agent layer (A) expands and forms the thermoplastic heat-expandable adhesive layer (A1); and step [4], the thermoplastic heat-expandable adhesive layer (A1) or the adhesive layer (B) constituting the aforementioned adhesive tape is pasted Attached to other parts (c1-2) or other adherends (C2) constituting the aforementioned adherend (C1).

In the aforementioned step [1], the thermoplastic heat-expandable adhesive layer (A) or the adhesive layer (B) of the adhesive tape is crimped to the adherend (C1) with a force of 0.1N/cm ² or more The part (c1-1) will increase the adhesive force of the aforementioned adhesive tape to the part (c1-1) that constitutes the adherend (C1), and it can suppress the deviation of the adhesive tape and the adherend (C1) even before heating , So better.

When crimping the thermoplastic heat-expandable adhesive layer (A) or the adhesive layer (B) of the adhesive tape to the part (c1-1) constituting the adherend (C1), it can be used as needed Equipment such as presses and rollers can also be pressed by fingers.

The heating temperature in the aforementioned step [2] is preferably, for example, a temperature corresponding to the temperature at which the expansion agent starts to expand (expansion start temperature). Specifically, it is preferably 50 to 150°C, more preferably 60 to 145°C, and 70 At ~140°C, the storage stability is excellent, and the aforementioned adhesive tape can be fully expanded without damaging the adherend with low heat resistance, and excellent adhesion can be obtained after expansion, so it is preferable.

The aforementioned heating method includes, for example, a method of putting an article into a heating device such as an oven, a heating furnace, and heating the entire article, by bringing a heat source into contact with or close to the thermoplastic thermally expandable adhesive layer (A) or the aforementioned adhesive tape Or a method of heating the thermoplastic heat-expandable adhesive layer (A) with the adherend.

As the aforementioned heat source, for example, a halogen lamp, a laser irradiation device, an electromagnetic induction heating device, a hot stamper, a hot plate, a soldering iron, etc. can be used. The heating method can be selected according to the size of the item.

The adhesive tape of the present invention preferably expands in the thickness direction after the aforementioned heating, and preferably does not expand substantially in the traveling direction or the width direction.

The aforementioned step [2] expands the aforementioned thermoplastic heat-expandable adhesive layer (A) to form a thermoplastic heat-expandable adhesive layer (A1) (step [3]). The aforementioned expansion causes the plastic heat-expandable adhesive layer (A1) to expand mainly in the thickness direction of the adhesive tape.

In the foregoing step [4], the force generated by the expansion of the thermoplastic heat-expandable adhesive layer (A) causes the adhesive layer (A1) or the adhesive layer (B) to form the same The other parts (c1-2) of the adherend (C1) or the adherend (C2) are crimped. Therefore, the voids in the adherend (C1), or the adherend (C1) When filling the gap with the adherend (C2), there is no need to use a press, for example, to apply pressure. In addition, the force generated by the aforementioned expansion will make the adhesive tape adhere to the adherend, so even if the surface is uneven (things with rough surfaces) as the adherend, it is not easy to get between the adhesive tape and the adherend. Form a gap.

The aforementioned adherends (C1) and (C2) include, for example, metals such as glass and aluminum, and plastics composed of resins such as acrylic and polycarbonate. The aforementioned adherends (C1) and (C2) can be made of the same material and shape, or can be made of different materials and shapes.

Regarding the adherends (C1) and (C2), the surfaces in contact with the thermoplastic thermally expandable adhesive layer (A) and the adhesive layer (B) may be rough surfaces.

The shapes of the adherend (C1) and the adherend (C2) are not particularly defined, and examples include two-dimensional shapes, three-dimensional shapes (curved surfaces, etc.), shapes with uneven surfaces, and fitting shapes. It can also be a combination of the above shapes.

The adhesive tape of the present invention can be expanded by applying heat to the thermoplastic heat-expandable adhesive layer (A) or the entire adhesive tape.

If the manufacturing method of the aforementioned article is carried out in the order of the aforementioned step [1], step [2] and step [3], it will have excellent adhesive force before heating, and can expand by heating, and it will appear after heating and expansion. The viewpoint of excellent adhesion is preferable. In particular, when the surface of the adherend (C1) or (C2) is rough, it is effective from the viewpoint of showing good adhesion.

For example, even if you want to use an adhesive tape that is pre-heated and expanded through step [2] at the beginning, it can still reduce the formation of fine gaps on the interface when attaching an adherend with uneven surface. The possibility.

Examples of articles obtained by the aforementioned method include small motors mounted on movable parts of automobiles. The aforementioned motor is generally composed of an exterior member (a cylindrical member) and a cover member. Specifically, the aforementioned motor includes a metal cylindrical member and a resin-made lid member corresponding to the shape of the cylindrical member and fixed in a fitted state. The adhesive tape of the present invention can fill the gap sometimes formed between the cylindrical member and the cover member.

[Example]

(Preparation Example 1)

<Preparation of Adhesive Composition (a-1)>

The styrene-butadiene block copolymer S (a mixture of triblock copolymer and diblock copolymer) with a weight average molecular weight of 300,000. Relative to the total amount of the aforementioned mixture, the aforementioned diblock copolymer accounts for The ratio is 50% by mass. In the entire styrene-butadiene block copolymer, the mass ratio of polystyrene units is 30% by mass, and the mass ratio of polybutadiene units is 70% by mass. ) 100 parts by mass and 65 parts by mass of the terpene phenol-based adhesion-imparting resin (softening point 115°C, molecular weight 1000) were mixed and dissolved in toluene, thereby obtaining the adhesive composition (a-1).

(Preparation Example 2)

<Preparation of Adhesive Composition (a-2)>

The amount of the terpene phenol-based adhesion-imparting resin (softening point 115°C, molecular weight 1000) used in Preparation Example 1 was changed from 65 parts by mass to 100 parts by mass, except that the adhesive was obtained in the same manner as in Preparation Example 1. Adhesive composition (a-2).

(Preparation Example 3)

<Preparation of Adhesive Composition (a-3)>

A styrene-isoprene block copolymer T (a mixture of triblock copolymer and diblock copolymer) with a weight average molecular weight of 200,000 is used. Relative to the total amount of the aforementioned mixture, the aforementioned diblock copolymer accounts for The ratio is 52% by mass. In the entire styrene-isoprene block copolymer, the mass ratio of polystyrene units is 15% by mass, and the mass ratio of polyisoprene units is 85 mass%) 100 mass parts instead of styrene-butadiene block copolymer S, using C5 petroleum-based adhesive resin (softening point 100℃, number average molecular weight 885) 40 mass parts, polymerized rosin ester-based adhesive resin (Softening point 125°C, number average molecular weight 880) 30 parts by mass, and 5 parts by mass of HV-100 (made by JX Nippon Oil & Energy Co., Ltd., low molecular weight polybutene) as a liquid adhesive resin instead of terpene Except for the enephenol-based adhesion-imparting resin, the adhesive composition (a-3) was obtained in the same manner as in Preparation Example 1.

(Preparation Example 4)

<Preparation of Adhesive Composition (a-4)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 44.9 parts by mass of butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid, and 3 parts by mass of vinyl acetate Parts by mass, 0.1 parts by mass of 4-hydroxybutyl acrylate, 0.1 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, dissolved in 100 parts by mass of ethyl acetate, and polymerized at 70°C for 10 hours, Thereby, an acrylic copolymer W solution with a weight average molecular weight of 800,000 was obtained.

Then, 30 parts by mass of polymerized rosin ester adhesive resin D-135 (manufactured by Arakawa Chemical Industry Co., Ltd.) was added to 100 parts by mass of acrylic copolymer W, and ethyl acetate was added and mixed to obtain non-volatile Adhesive composition (a-4) of 45% by mass of sexual components.

(Preparation Example 5)

<Preparation of Adhesive Composition (a-5)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 95.5 parts by mass of butyl acrylate, 4 parts by mass of acrylic acid, and 0.5 parts by mass of hydroxyethyl acrylate were used as the polymerization initiator. 0.2 parts by mass of 2'-azobisisobutyronitrile was dissolved in 100 parts by mass of ethyl acetate and polymerized at 80°C for 8 hours, thereby obtaining an acrylic copolymer solution X with a weight average molecular weight of 650,000.

Then, to 100 parts by mass of the acrylic copolymer X, 10 parts by mass of rosin ester resin A-100 (manufactured by Arakawa Chemical Co., Ltd.) and polymerized rosin ester resin D-135 (manufactured by Arakawa Chemical Co., Ltd.) were added. 20 parts by mass was added and mixed with toluene to obtain an adhesive composition (a-5) with a non-volatile content of 45% by mass.

(Preparation Example 6)

<Preparation of Adhesive Composition (a-6)>

The amount of the terpene phenol-based adhesion-imparting resin (softening point 115°C, molecular weight 1000) used in Preparation Example 1 was changed from 65 parts by mass to 5 parts by mass, except that the adhesive was obtained in the same manner as in Preparation Example 1. Adhesive composition (a-6).

(Preparation Example 7)

<Preparation of Adhesive Composition (a-7)>

EPICLON N-680 (cresol novolac epoxy resin solution manufactured by DIC Co., Ltd., epoxy equivalent 215g/eq, non-volatile content 75% by mass) 21.4 parts by mass, and "YL-7862" (Mitsubishi Epoxy resin manufactured by Chemical Co., Ltd., epoxy equivalent 3748g/eq, non-volatile content 50% by mass) 48 parts by mass are mixed, then 30.6 parts by mass of methyl ethyl ketone is mixed to obtain 40% by mass of non-volatile content Epoxy resin composition Y.

Then, 0.4 parts by mass of Curezol 2MAOK-PW (manufactured by Shikoku Kasei Co., Ltd., imidazole-based curing accelerator) as a curing agent was mixed with 100 parts by mass of the aforementioned epoxy resin composition Y, and stirred for 10 minutes, thereby The adhesive composition (a-7) was obtained.

<Preparation of Adhesive Composition (a-8)>

The amount of the terpene phenol-based adhesion-imparting resin (softening point 115°C, molecular weight 1000) used in Preparation Example 1 was changed from 65 parts by mass to 20 parts by mass, and the adhesive was obtained by the same method as Preparation Example 1, except that Adhesive composition (a-8).

<Making of Adhesive Tape>

(Example 1)

Use a rod-shaped metal applicator to mix 100 parts by mass of the total solid content of the adhesive composition (a-1) as an expansion agent, Matsumoto Microsphere F-36D (manufactured by Matsumoto Oil and Fat Co., Ltd., thermally expandable) Microcapsules, initial particle size 10-16μm, expansion start temperature 70-80℃) 10 parts by mass, stirred for 10 minutes, and coated on both sides of high-quality paper so that the thickness after drying becomes 60μm. The surface of a 130μm-thick release paper with a ethylene layer and a silicone-based release treatment agent layer on one side of the polyethylene layer is dried with a dryer set at 65°C for 10 minutes to produce thermoplastic thermal expansion Adhesive layer (A-1). Laminate the aforementioned thermoplastic heat-expandable adhesive layer (A-1) on another release paper different from the above, and use a 2kg hand roller to move it back and forth on the upper surface of the aforementioned sticker once. An adhesive tape composed of the aforementioned thermoplastic heat-expandable adhesive layer (A-1) was obtained.

(Example 2)

Except that the adhesive composition (a-2) was used instead of the adhesive composition (a-1), the same method as in Example 1 was used to obtain a thermoplastic thermally expandable adhesive layer (A-2) Composition of sticky tape.

(Example 3)

Except that the adhesive composition (a-3) was used instead of the adhesive composition (a-1), the same method as in Example 1 was used to obtain a thermoplastic thermally expandable adhesive layer (A-3) Composition of sticky tape.

(Example 4)

Using a rod-shaped metal applicator, the adhesive composition (a-4) 1 (00 parts by mass) was diluted with toluene until the non-volatile components therein became 30% by mass, stirred for 10 minutes, and then added as expansion 10 parts by mass of F-36D of the agent and stirring for 10 minutes, apply it to the top-quality paper with a polyethylene layer on both sides and polysiloxane on one side of the polyethylene layer so that the thickness after drying becomes 60μm The surface of a release paper with a thickness of 130μm, which is a release treatment agent layer, is dried with a dryer set at 65°C for 10 minutes to produce a thermoplastic heat-expandable adhesive layer (A-4). In the same manner as in Example 1, an adhesive tape composed of a thermoplastic heat-expandable adhesive layer (A-4) was obtained.

(Example 5)

Except that the adhesive composition (a-5) was used instead of the adhesive composition (a-4), the same method as in Example 4 was used to obtain a thermoplastic thermally expandable adhesive layer (A-5) Composition of sticky tape.

(Example 6)

The thermoplastic heat-expandable adhesive layer (A-1) was produced in the same manner as in Example 1.

Then, using a rod-shaped metal applicator, the aforementioned adhesive composition (a-1) was applied to a sheet with a polyethylene layer on both sides of the high-quality paper so that the thickness after drying became 60 μm. Face with The surface of the release paper with a thickness of 130 μm with a silicone-based release treatment agent layer was dried with a dryer set at 65° C. for 10 minutes to form an adhesive layer (B-1).

Attach the adhesive layer (B-1) to the thermoplastic heat-expandable adhesive layer (A-1) obtained above, and use a 2kg hand roller to make it back and forth on the upper surface of the adhesive once. This obtained an adhesive tape obtained by laminating the adhesive layer (B-1) on one side of the thermoplastic heat-expandable adhesive layer (A-1).

(Example 7)

Except that the adhesive composition (a-2) was used instead of the adhesive composition (a-1), the same method as in Example 6 was used to produce a thermoplastic thermally expandable adhesive layer (A-2) and Adhesive layer (B-2), and an adhesive tape obtained by laminating an adhesive layer (B-2) on one side of the aforementioned thermoplastic heat-expandable adhesive layer (A-2).

(Example 8)

The adhesive composition (a-3) was used instead of the adhesive composition (a-1), except that the same method as in Example 6 was used to produce a thermoplastic thermally expandable adhesive layer (A-3) And an adhesive layer (B-3), and an adhesive tape obtained by laminating an adhesive layer (B-3) on one side of the aforementioned thermoplastic thermally expandable adhesive layer (A-3).

(Example 9)

The adhesive composition (a-4) was used instead of the adhesive composition (a-1), except that the same method as in Example 6 was used to produce a thermoplastic thermally expandable adhesive layer (A-4) And an adhesive layer (B-4), and an adhesive tape obtained by laminating an adhesive layer (B-4) on one side of the aforementioned thermoplastic thermally expandable adhesive layer (A-4).

(Example 10)

Except that the adhesive composition (a-5) was used instead of the adhesive composition (a-1), the same method as in Example 6 was used to produce a thermoplastic thermally expandable adhesive layer (A-5) And an adhesive layer (B-5), and an adhesive tape obtained by laminating an adhesive layer (B-5) on one side of the thermoplastic heat-expandable adhesive layer (A-5).

(Example 11)

The thermoplastic heat-expandable adhesive layer (A-1) is attached to one side of a 12μm thick polyethylene terephthalate film, and the adhesive layer (B-1) obtained above is attached to the other side , And then press and laminate at 4kgf/cm ² to obtain a thermoplastic thermally expandable adhesive layer (A-1) and adhesive layer (B-1) laminated on a polyethylene terephthalate film Made of adhesive tape.

(Example 12)

Use thermoplastic heat-expandable adhesive layer (A-2) instead of thermoplastic heat-expandable adhesive layer (A-1), and use adhesive layer (B-2) instead of adhesive layer (B-1), Except for this, a polyethylene terephthalate film laminated with a thermoplastic thermally expandable adhesive layer (A-2) and an adhesive layer (B-2) was obtained in the same manner as in Example 11. Sticky tape.

(Example 13)

Use thermoplastic heat-expandable adhesive layer (A-3) instead of thermoplastic heat-expandable adhesive layer (A-1), and use adhesive layer (B-3) instead of adhesive layer (B-1), Except for this, a polyethylene terephthalate film laminated with a thermoplastic thermally expandable adhesive layer (A-3) and an adhesive layer (B-3) was obtained in the same manner as in Example 11. Sticky tape.

(Example 14)

Use the thermoplastic heat-expandable adhesive layer (A-4) to replace the thermoplastic heat-expandable adhesive layer (A-1), and use the adhesive layer (B-4) to replace the adhesive layer (B-1), Except for this, a polyethylene terephthalate film laminated with a thermoplastic thermally expandable adhesive layer (A-4) and an adhesive layer (B-4) was obtained in the same manner as in Example 11. Sticky tape.

(Example 15)

Use a thermoplastic heat-expandable adhesive layer (A-5) instead of the thermoplastic heat-expandable adhesive layer (A-1), and use an adhesive layer (B-4) instead of the adhesive layer (B-5), Except for this, a polyethylene terephthalate film laminated with a thermoplastic thermally expandable adhesive layer (A-5) and an adhesive layer (B-5) was obtained in the same manner as in Example 15. Sticky tape.

(Example 16)

Attach the thermoplastic heat-expandable adhesive layer (A-1) to one side of the non-woven fabric with a thickness of 35μm, and attach the adhesive layer (B-1) obtained above on the other side, and then apply 4kgf/ cm ² is laminated under pressure to obtain an adhesive tape formed by laminating a thermoplastic thermally expandable adhesive layer (A-1) and an adhesive layer (B-1) on the nonwoven fabric.

(Example 17)

Use thermoplastic heat-expandable adhesive layer (A-2) instead of thermoplastic heat-expandable adhesive layer (A-1), and use adhesive layer (B-2) instead of adhesive layer (B-1), Except for this, an adhesive tape obtained by laminating a thermoplastic thermally expandable adhesive layer (A-2) and an adhesive layer (B-2) on a nonwoven fabric was obtained in the same manner as in Example 16.

(Example 18)

Use thermoplastic heat-expandable adhesive layer (A-3) instead of thermoplastic heat-expandable adhesive layer (A-1), and use adhesive layer (B-3) instead of adhesive layer (B-1), Except for this, an adhesive tape obtained by laminating a thermoplastic thermally expandable adhesive layer (A-3) and an adhesive layer (B-3) on a nonwoven fabric was obtained in the same manner as in Example 16.

(Example 19)

Use the thermoplastic heat-expandable adhesive layer (A-4) to replace the thermoplastic heat-expandable adhesive layer (A-1), and use the adhesive layer (B-4) to replace the adhesive layer (B-1), Except for this, an adhesive tape obtained by laminating a thermoplastic thermally expandable adhesive layer (A-4) and an adhesive layer (B-4) on a nonwoven fabric was obtained in the same manner as in Example 16.

(Example 20)

Use the thermoplastic heat-expandable adhesive layer (A-5) to replace the thermoplastic heat-expandable adhesive layer (A-1), and use the adhesive layer (B-5) to replace the adhesive layer (B-1), Except for this, an adhesive tape obtained by laminating a thermoplastic thermally expandable adhesive layer (A-5) and an adhesive layer (B-5) on a nonwoven fabric was obtained in the same manner as in Example 16.

(Example 21)

Instead of using F-36D, Expancel 051-40 (manufactured by Japan Fillite Co., Ltd., heat-expandable microcapsules, initial particle size 12μm, expansion starting temperature 110°C) was used as the expansion agent. Otherwise, the same as in Example 6 In the same way, an adhesive tape obtained by laminating the adhesive layer (B-1) on one side of the thermoplastic heat-expandable adhesive layer (A-6).

(Example 22)

Except that the adhesive composition (a-6) was used instead of the adhesive composition (a-1), the same method as in Example 6 was used to obtain the thermoplastic heat-expandable adhesive layer (A-7) Adhesive tape made of single-sided laminated adhesive layer (B-1).

(Example 23)

Except that the adhesive composition (a-8) was used instead of the adhesive composition (a-1), the same method as in Example 6 was used to obtain the thermoplastic heat-expandable adhesive layer (A-13) Adhesive tape made of single-sided laminated adhesive layer (B-1).

(Example 24)

Instead of using F-36D, use F-30 (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., thermally expandable microcapsules, initial particle size 10~16μm, expansion start temperature 70~80°C) as the expansion agent. In addition, use In the same manner as in Example 6, an adhesive tape obtained by laminating the adhesive layer (B-1) on one side of the thermoplastic heat-expandable adhesive layer (A-14) was obtained.

(Example 25)

Instead of using F-36D, use Expancel 031-40 (manufactured by Japan Fillite Co., Ltd., thermally expandable microcapsules, initial particle size 10μm~16μm, expansion start temperature 80~95℃) as the expansion agent. In addition, use In the same manner as in Example 6, an adhesive tape obtained by laminating the adhesive layer (B-1) on one side of the thermoplastic heat-expandable adhesive layer (A-15) was obtained.

(Example 26)

With respect to 100 parts by mass of the total solid content of the adhesive composition (a-2), 5 parts by mass of F-36D as an expansion agent were mixed, except that the same method as in Example 2 was used to obtain a thermoplastic heat-expandable bonding Adhesive tape composed of agent layer (A-16).

(Example 27)

With respect to 100 parts by mass of the total solid content of the adhesive composition (a-2), 15 parts by mass of F-36D as an expansion agent were mixed, except that the same method as in Example 2 was used to obtain a thermoplastic heat-expandable bonding Adhesive tape composed of agent layer (A-17).

(Example 28)

30 parts by mass of F-36D as an expansion agent was mixed with 100 parts by mass of the total solid content of the adhesive composition (a-2), except that the same method as in Example 2 was used to obtain a thermoplastic thermally expandable bonding Adhesive tape composed of agent layer (A-17).

(Comparative example 1)

Except that the expansion agent F-36D was not used, an adhesive tape composed of an adhesive layer (A-8) was obtained in the same manner as in Example 1.

(Comparative example 2)

Except that the expansion agent F-36D was not used, an adhesive tape composed of an adhesive layer (A-9) was obtained in the same manner as in Example 2.

(Comparative example 3)

Except that the expansion agent F-36D was not used, an adhesive tape composed of an adhesive layer (A-10) was obtained in the same manner as in Example 3.

(Comparative Example 4)

Except that the expansion agent F-36D was not used, an adhesive tape composed of an adhesive layer (A-11) was obtained in the same manner as in Example 4.

(Comparative Example 5)

Except that the expansion agent F-36D was not used, an adhesive tape composed of an adhesive layer (A-12) was obtained in the same manner as in Example 5.

(Comparative Example 6)

Using a rod-shaped metal applicator, mix 100 parts by mass of the adhesive composition (a-7) with 3.2 parts by mass of Expancel 051-40 as an expansion agent and stir for 10 minutes to obtain the thickness after drying It is applied to the surface of a release film obtained by peeling a polysiloxane compound on one side of a polyethylene terephthalate film with a thickness of 75 μm in a way of becoming 50μm, and then using a dryer set at 75°C Dry for 10 minutes to form an adhesive layer (A-13). The adhesive layer (A-13) is attached to the release film, and a 2kg hand roller is used to make it back and forth on the upper surface of the adhesive once to obtain the adhesive layer (A -13) Adhesive tape composed of.

[Measurement method of storage elastic modulus of thermally expandable adhesive layer]

Use an applicator to apply the adhesive compositions (a-1) to (a-6) and (a-8) prepared in Preparation Examples 1 to 6 and 8 to the adhesive so that the thickness after drying becomes 100 μm. The surface of the mold pad was dried at 85°C for 5 minutes to form multiple adhesive layers each with a thickness of 100μm.

Then, the adhesive layers obtained by using the same adhesive were superimposed, thereby respectively producing test pieces composed of adhesive layers with a thickness of 2 mm.

A parallel plate with a diameter of 7.9 mm was mounted on a viscoelasticity tester (ARES 2kSTD) manufactured by TA Instruments Japan Co., Ltd. Use the aforementioned parallel plate to clamp the aforementioned test piece with a compressive load of 40~60g, and measure the storage elastic modulus (G23) at 23°C under the conditions of a frequency of 1Hz, a temperature range of -60~150°C, and a heating rate of 2°C/min. ) And the storage elastic modulus (G70) at 70°C and the storage elastic modulus (G120) at 120°C. In addition, for Comparative Example 6, since a thermosetting resin was used, the aforementioned measurement method could not be applied, so it was not measured.

〔Method for measuring the initial adhesion of thermally expansive adhesive layer〕

According to JIS Z 0237, the 180-degree peel adhesion was measured.

For Examples 6-22, the release pad on the adhesive layer (B) side of the adhesive tape was peeled off, and the adhesive layer was backed by a polyethylene terephthalate film with a thickness of 25 μm. For others, the surface on which the release gasket is to be stripped is not specifically specified. After cutting the aforementioned backed adhesive tape into a width of 20mm, peel off the mold release pad on the side of the thermoplastic heat-expandable adhesive layer (A) of the adhesive tape, and attach the adhesive layer to the SUS board. Degrease the smooth surface and roll it back and forth once with a 2kg roller. The one obtained in this way will be used as a test piece.

After placing the aforementioned test piece in an environment of 23°C for 1 hour, in the same environment, use a Tensilon tensile testing machine [manufactured by A&D Co., Ltd., model: RTM-100] to measure the double-sided adhesion of the aforementioned test piece. Adhesive force when the tape is peeled from the SUS board along the 180 degree direction at a speed of 300 mm/min.

[Adhesive tape and method for measuring the expansion rate of each adhesive layer constituting the adhesive tape]

The thickness of the adhesive tape manufactured by the aforementioned method and the thickness of each adhesive layer constituting the adhesive tape were measured using a thickness meter.

In addition, the adhesive tape was swelled by placing it in an environment of 100°C for 30 minutes.

In addition, for Example 21, it was swelled by placing it in an environment of 120°C for 30 minutes, and for Comparative Example 6, it was swelling by placing it in an environment of 130°C for 1 hour.

Then, the thickness of the adhesive tape after expansion and the thickness of the adhesive layer constituting the adhesive tape were measured using a thickness meter.

The aforementioned expansion rate is calculated according to the following formula to calculate the ratio of the thickness of the adhesive tape after placing the aforementioned adhesive tape in an environment of 100°C for 30 minutes to the thickness of the aforementioned adhesive tape before placing (before expansion), and due to the aforementioned The ratio of the thickness of the thermoplastic heat-expandable adhesive layer (A1) formed by the expansion of the aforementioned thermoplastic heat-expandable adhesive layer (A) to the thickness of the thermoplastic heat-expandable adhesive layer (A) before the placement, And the ratio of the thickness of the adhesive layer (B) after the placement to the thickness of the adhesive layer (B) before the placement.

〔The thickness of the adhesive tape after placing (after expansion)/the thickness of the adhesive tape before placing (before expansion)×100%

[Thickness of the expanded thermoplastic heat-expandable adhesive layer (A) [thermoplastic heat-expandable adhesive layer (A1)] constituting the adhesive tape after placement (after expansion) / composition before placement (before expansion) The thickness of the thermoplastic heat-expandable adhesive layer (A) of the adhesive tape]×100%

[The thickness of the adhesive layer (B) that constitutes the adhesive tape after placement/the thickness of the adhesive layer (B) that constitutes the adhesive tape before placement] × 100%

〔Method for measuring the expansion rate of adhesive layer (A) 2〕

Place the adhesive tape in an environment of 85°C for 30 minutes. Except for this, the adhesive tape and the method of measuring the expansion rate of each adhesive layer constituting the adhesive tape were used to measure the adhesiveness of Examples 1 to 5. Expansion rate of the adhesive layer (A).

[Evaluation method of void filling property]

Degrease two aluminum plates with a width of 15mm × a length of 70mm × a thickness of 0.5mm with smooth surfaces. The two spacers (3 of Figure 1) are arranged in parallel with an interval of 12mm and bonded with adhesive tape (50μm). The end of the upper surface (C1-1) of an aluminum plate (C1) (No. 1 in Figure 1). The aforementioned spacer was prepared in such a way that the total thickness of the spacer and the adhesive tape used for bonding was 60 μm thicker than the total thickness of each adhesive tape made in Examples 1-28 and Comparative Examples 1-5 Become.

Then, on the upper surface (C1-1) side of the aluminum plate (C1) and between the two spacers, an adhesive tape cut into a size of 10mm×10mm was attached (for Examples 6-22, it is Attach the surface corresponding to the aforementioned thermoplastic heat-expandable adhesive layer (A)), and use a 2kg hand roller to press it. There are no special regulations on the sticking surface of Examples 1 to 5 and Comparative Examples 1 to 6.

Then, on the upper surface of the aforementioned adhesive tape (for Examples 6-25, it is the surface equivalent to the aforementioned adhesive layer (B)), another aluminum plate (C2) (width 15mm×length 70mm×thickness 0.5mm), and fix them with clips.

After the above-mentioned fixed body is heated at 100°C for 30 minutes, it is placed in an environment of 23°C for 30 minutes to cool. In addition, for Example 21, it was heated at 120°C for 30 minutes, and for Comparative Example 6, it was heated at 130°C for 1 hour, and then placed in an environment of 23°C for 30 minutes to cool.

Then, remove the aforementioned clip and pick up the end of the aluminum plate (C2). At this time, the aluminum plate (C1) that did not fall was rated as "○", and the one that fell was rated as "×".

[Measurement method of shear adhesion 1]

The same thing as the evaluation of void filling was produced. After heating at 100°C for 30 minutes, it was left in an environment of 23°C for 30 minutes to cool, and then the clip was removed. In addition, for Example 21, it was heated at 120°C for 30 minutes, and for Comparative Example 6, it was heated at 130°C for 1 hour, then placed in an environment of 23°C for 30 minutes to cool, and then the clip was removed.

The test pieces were clamped to the ends of the two aluminum plates respectively, and a tensile test was performed using a tensile testing machine along a 180 degree direction at a tensile speed of 10 mm/min to obtain the adhesive force of the adhesive tape.

[Measurement method of shear adhesion 2]

For the aforementioned spacers, a method was used so that the total thickness of the spacer and the adhesive tape used for bonding was 120μm thicker than the total thickness of the adhesive tapes made in Examples 1-28 and Comparative Examples 1-5 Except for the prepared product, the measurement is carried out in the same manner as the measurement method of the shear adhesive force 1.

〔Method for measuring shear adhesion force 3〕

Examples 1 to 5 were used to prepare test pieces similar to the evaluation of void filling properties. After heating at 85°C for 30 minutes, they were placed in an environment of 23°C for 30 minutes to cool down, and then the clip was removed. Audition. Furthermore, for the aforementioned spacer, the total thickness of the spacer and the adhesive tape used for bonding was prepared in such a way that the total thickness of each adhesive tape made in Examples 1 to 5 was 30 μm thicker, and The measurement is performed in the same way as the measurement method of shear adhesion 1.

[Measurement method of shear adhesion 4]

Using Examples 6 to 10, on the upper surface (C1-1) side of the aluminum plate (C1) and between the aforementioned two spacers, the adhesive layer of the adhesive tape cut into the size of 10mm×10mm was attached (B) Except for this, the measurement is performed by the same method as the measurement method of shear adhesion 1.

〔Component selection〕

Using the adhesive tapes produced in Examples 1 to 28 and Comparative Examples 1 to 6, and using an aluminum plate and an acrylic plate, respectively, test pieces similar to the evaluation of void filling properties were produced. (Acrylic board: 2 sheets of acrylic board with a width of 15mm×length 70mm×thickness 1.5mm are degreased, and the two spacers are arranged in parallel at an interval of 12mm and glued with adhesive tape (50μm) The end of the upper surface (D1-1) of an acrylic plate (D1) connected to it. The aforementioned spacer is used so that the total thickness of the spacer and the adhesive tape used for bonding is compared with that of Example 1. ~28 and Comparative Examples 1 to 5 are prepared in such a way that the total thickness of each adhesive tape is 60μm thick.

Then, on the upper surface (D1-1) side of the acrylic plate (D1) and between the two spacers, stick an adhesive tape that has been cut into a size of 10mm×10mm (for example 6~ 22 is to affix the surface corresponding to the aforementioned thermoplastic heat-expandable adhesive layer (A)), and use a 2kg hand roller for crimping. Then, on the upper surface of the aforementioned adhesive tape (for Examples 6-22, it is the surface equivalent to the aforementioned adhesive layer (B)), another acrylic plate (D2 ) (Width 15mm×Length 70mm×Thickness 1.5mm), and fix them with clips. )

After heating the aforementioned test piece at 100°C for 30 minutes, it was placed in an environment of 23°C for 30 minutes to cool. In addition, for Example 22, after heating at 130°C for 30 minutes, it was left in an environment of 23°C for 30 minutes to cool. Then, remove the aforementioned clip and pick up the ends of the aluminum plate (C2) and acrylic plate (C2). At this time, the aluminum plate (C1) and acrylic plate (D1) did not fall and the deformation of the aluminum plate and the acrylic plate was rated as "○". Although the aluminum plate (C1) and acrylic plate were observed Those who are deformed are rated as "△", and those who fail are rated as "×".

Claims (8)

A method of manufacturing an article by bonding or filling the gaps in the adherend (C1) or the gap between the adherend (C1) and the adherend (C2) by the expansion of the adhesive tape The method of manufacturing an article, wherein the adhesive tape has a thermoplastic heat-expandable adhesive layer (A) and at least one side of the thermoplastic heat-expandable adhesive layer (A) has an adhesive layer (B), the thermoplastic Expansion rate in the thickness direction of the heat-expandable adhesive layer (A) (the thickness of the thermoplastic heat-expandable adhesive layer (A1) after heating/the thickness of the thermoplastic heat-expandable adhesive layer (A) before heating)×100 % Is 150% or more. The thermoplastic heat-expandable adhesive layer (A) contains a thermoplastic resin and a heat-expandable capsule whose expansion start temperature is in the range of 50°C to 150°C. The thermoplastic resin has dynamic viscoelasticity at 70°C and 1Hz The storage elastic modulus G ₇₀ measured by the spectrum is in the range of 1.0×10 ² Pa~5.0×10 ⁶ Pa, and the storage elastic modulus G ₁₂₀ measured by the dynamic viscoelastic spectrum at 120°C and 1 Hz of the thermoplastic resin is 1.0×10 ^{In the range of 2} Pa~2.0×10 ⁵ Pa, the content of the heat-expandable capsule is in the range of 0.3 parts by mass to 17 parts by mass relative to 100 parts by mass of the solid content in all components of the thermoplastic heat-expandable adhesive layer (A); The manufacturing method of the article includes the following steps in order: step [1], attach the thermoplastic heat-expandable adhesive layer (A) or adhesive layer (B) of the adhesive tape to the adherend (C1) Part (c1-1); step [2], heating the thermoplastic thermally expandable adhesive layer (A) at a temperature of 50°C to 150°C; step [3], heating the thermoplastic thermally expandable adhesive layer The agent layer (A) expands and forms a thermoplastic heat-expandable adhesive layer (A1); and step [4], the thermoplastic heat-expandable adhesive layer (A1) or the adhesive layer (B) constituting the adhesive tape is pasted Attached to other parts (c1-2) or other adherends (C2) constituting the adherend (C1). For example, the manufacturing method of article 1 in the scope of the patent application, wherein the expansion rate of the adhesive layer (B) in the thickness direction [the thickness of the adhesive layer (B1) after heating/the adhesive layer before heating (B) Thickness]×100% is 120% or less. For example, the method for manufacturing an article in the scope of the patent application, wherein the thermoplastic heat-expandable adhesive layer (A) is attached to the adhesive layer (A1) before being heated to form the thermoplastic heat-expandable adhesive layer (A1) Adhesive layer of body (C1). For example, the method for manufacturing an article according to any one of items 1 to 3 in the scope of the patent application, wherein the thermoplastic heat-expandable adhesive layer (A) has an adhesive force of 0.5N/20mm or more. For example, the manufacturing method of article 1 in the scope of the patent application, wherein the step [1] includes the following steps: crimping the thermoplastic heat-expandable adhesive layer (A) of the adhesive tape with a force of 0.1 N/cm ² or more In the part (c1-1) that constitutes the adherend (C1). For example, the manufacturing method of the article 1 or 5 in the scope of the patent application, wherein the step [4] includes the following steps: the thermoplastic heat expands by the force generated by the expansion of the thermoplastic heat expandable adhesive layer (A) The adhesive layer (A1) or the adhesive layer (B), and other parts (c1-2) constituting the adherend (C1) or other adherends (C2) are crimped. A method for filling the voids of the adherend (C1), or the voids between the adherend (C1) and the adherend (C2), includes the following steps in order: Step [1], the adhesive with thermoplastic thermal expansion Adhesive layer (A) and the thermoplastic heat-expandable adhesive layer (A) of the adhesive tape having an adhesive layer (B) on at least one side of the thermoplastic heat-expandable adhesive layer (A) is attached to the composition The part (c1-1) of the adherend (C1), where the expansion ratio in the thickness direction of the thermoplastic heat-expandable adhesive layer (A) [the thickness of the thermoplastic heat-expandable adhesive layer (A1) after heating/ The thickness of the thermoplastic heat-expandable adhesive layer (A) before heating]×100% is 150% or more. The thermoplastic heat-expandable adhesive layer (A) contains a thermoplastic resin and has an expansion start temperature of 50°C to 150°C. The range of thermal expansion capsules, the storage elastic modulus G ₇₀ of the thermoplastic resin measured by dynamic viscoelastic spectrum at 70℃ at 1Hz is in the range of 1.0×10 ² Pa~5.0×10 ⁶ Pa, and the thermoplastic resin’s temperature at 120℃ The storage elastic modulus G ₁₂₀ measured by dynamic viscoelastic spectrum at 1 Hz is in the range of 1.0×10 ² Pa~2.0×10 ⁵ Pa. The content of the heat-expandable capsule is relative to all the components of the thermoplastic heat-expandable adhesive layer (A) 100 parts by mass of the solid content in the compound is within the range of 0.3 parts by mass to 17 parts by mass; step [2], heating the thermoplastic thermally expandable adhesive layer (A); step [3], thermally expanding the thermoplastic by the heating Adhesive layer (A) expands to form a thermoplastic heat-expandable adhesive layer (A1); and step [4], the thermoplastic heat-expandable adhesive layer (A1) or adhesive layer ( B) Attach to other parts (c1-2) or other adherends (C2) constituting the adherend (C1). An article obtained by the manufacturing method of any one of items 1 to 6 in the scope of the patent application.

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