WO2016170593A1 - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- WO2016170593A1 WO2016170593A1 PCT/JP2015/062059 JP2015062059W WO2016170593A1 WO 2016170593 A1 WO2016170593 A1 WO 2016170593A1 JP 2015062059 W JP2015062059 W JP 2015062059W WO 2016170593 A1 WO2016170593 A1 WO 2016170593A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- polyurethane resin
- sheet according
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
Definitions
- the present invention relates to a single-sided or double-sided pressure-sensitive adhesive sheet that can be peeled without any residue or breakage by extensive stretching within the adhesive surface.
- an adhesive sheet is used for fixing the battery pack and the casing. And when taking out a battery pack, an adhesive sheet is pulled and it peels by the extending
- the pressure-sensitive adhesive sheet for such use is required to have performance such as no residue (pressure-sensitive adhesive) remaining at the time of peeling and no destruction of the sheet.
- Patent Document 1 discloses a specific adhesive film piece in which the adhesiveness of the adhesive layer disappears when the film is stretched
- Patent Document 2 discloses a specific block copolymer.
- An adhesive sheet strip comprising a styrene block copolymer and an acid-modified and / or acid-modified elastomer is disclosed in US Pat.
- Patent Document 4 discloses an adhesive tape having a specific backing layer and a pressure-sensitive adhesive layer.
- the conventional pressure-sensitive adhesive sheet that can be peeled by stretching has room for further improvement in performance, such as no residue remaining at the time of peeling, and no destruction of the sheet.
- An object of the present invention is to provide a pressure-sensitive adhesive sheet in which a residue (pressure-sensitive adhesive) does not remain at the time of peeling by stretching and the sheet is not broken.
- the present inventors have found that it is very effective to use a specific urethane resin as the base polymer of the base material, and have completed the present invention.
- the present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side or both sides of a base material and capable of being peeled off by stretching, wherein the base material has a softening point of 60 ° C. or less according to JIS K 7196.
- a pressure-sensitive adhesive sheet obtained by using a resin as a base polymer.
- the base material since a specific urethane resin is used as the base polymer of the base material, appropriate flexibility, stretchability, and tensile strength are exhibited. As a result, the base material does not break even during peeling due to stretching. It becomes a pressure sensitive adhesive sheet.
- the base material used in the present invention is characterized in that a polyurethane resin having a softening point of 60 ° C. or lower is obtained as a base polymer.
- the softening point measured in accordance with JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis” is 60 ° C. or less, preferably 30 ° C. to 60 ° C.
- a pull test and a reworkability test were performed. These tests are tests for evaluating the performance that allows easy peeling without any problem when peeling the adhesive sheet in the bonded state.
- This invention provides the adhesive sheet which has the performance (rework property) that a base material does not destroy in such a test and there is no residue of an adhesive. For example, when taking out parts such as a battery pack of an information portable terminal such as a smartphone or a mobile phone, it is necessary to pull one end of the pressure-sensitive adhesive sheet and peel it off by stretching. At that time, it is desirable that the pressure-sensitive adhesive sheet can be easily peeled off and no residue such as a pressure-sensitive adhesive remains at the peeled portion.
- the pressure-sensitive adhesive layer within the adhesive surface is stretched uniformly and uniformly over a wide range by pulling one end of the pressure-sensitive adhesive sheet, and the adhesive strength is moderately reduced. As a result, no residue (adhesive) remains, and peeling can be easily performed. However, if the tensile strength of the substrate is low, the substrate may be destroyed. On the other hand, since a polyurethane resin having specific physical properties is used in the present invention, these problems are less likely to occur.
- the glass transition temperature (Tg) of the polyurethane resin is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 30 ° C. to ⁇ 10 ° C.
- Tg glass transition temperature
- the weight average molecular weight (Mw) of the polyurethane resin is preferably 100,000 to 300,000, more preferably 100,000 to 200,000.
- Mw weight average molecular weight
- the polyurethane resin is usually a polymer of a polyol and a polyfunctional isocyanate, and is a resin containing a soft segment composed of a polyol monomer unit and a hard segment composed of a polyfunctional isocyanate compound or a low molecular glycol monomer unit. .
- the polyol used for the polyurethane resin is a compound having two or more hydroxyl groups.
- the number of hydroxyl groups in the polyol is preferably 2 to 3, more preferably 2.
- polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, or castor oil-based polyol can be used. Two or more polyols may be used in combination.
- Polyester polyol is obtained, for example, by an esterification reaction between a polyol component and an acid component.
- the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Examples include methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexa
- the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1 , 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid
- acids and acid anhydrides thereof include acids and acid anhydrides thereof.
- Polyether polyols start with, for example, water, low molecular weight polyols (eg propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol), bisphenols (eg bisphenol A) or dihydroxybenzenes (eg catechol, resorcin, hydroquinone)
- low molecular weight polyols eg propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol
- bisphenols eg bisphenol A
- dihydroxybenzenes eg catechol, resorcin, hydroquinone
- alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide.
- Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
- polycaprolactone polyol examples include ring-opening polymers of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
- polycarbonate polyol examples include polycarbonate polyols obtained by polycondensation reaction of each of the above polyol components and phosgene; each of the above polyol components, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene Polycarbonate polyol obtained by transesterification condensation with carbonic acid diesters such as carbonate, propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymer polycarbonate polyol obtained by using two or more of each of the above polyol components; A polycarbonate polyol obtained by an esterification reaction with a carboxyl group-containing compound; each of the above polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate polyol obtained by etherification reaction; polycarbonate polyol obtained by transesterification of each of the above polycarbonate polyol and ester
- Castor oil-based polyol is obtained, for example, by reacting castor oil fatty acid with each of the above polyol components (for example, polypropylene glycol).
- polyfunctional isocyanate compound used in the polyurethane resin for example, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, or a polyfunctional aromatic isocyanate compound can be used. Trimethylolpropane adducts of these compounds, burettes reacted with water, and trimers having an isocyanurate ring can also be used. Two or more polyfunctional isocyanate compounds may be used in combination.
- polyfunctional aromatic diisocyanate compound examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, Examples include 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
- the polyurethane resin is obtained by curing the composition containing the polyol and the polyfunctional isocyanate compound described above.
- a low crystalline linear polyester polyurethane resin is preferable, and a hexanediol copolyester polyurethane resin and a polytetramethylene glycol polyurethane resin are more preferable.
- polyurethane resins examples include Desmocol (Registered Trademark) manufactured by Sumika Bayer Urethane Co., Ltd., and Nippon Polan (Registered Trademark) manufactured by Nippon Polyurethane Industry Co., Ltd.
- the low crystallinity is obtained by preparing a resin test piece having a thickness of 6 mm and melting the test piece at 100 ° C. for 30 minutes, 23 ⁇ 2 ° C., relative humidity This can be determined by measuring the time from when the resin is left in an environment of 50 ⁇ 5% until the hardness of the resin reaches Shore A90.
- a resin having a time period of 72 hours or longer until Shore A 90 is reached can be referred to as a low crystalline resin.
- a crosslinking agent from the viewpoint of improving the physical properties of the base polymer.
- a crosslinking agent for example, a metal chelate-based, metal alkoxide-based, epoxy-based, isocyanate-based, aziridine-based, polyfunctional acrylate, carbodiimide-based, oxazoline-based, or melamine-based crosslinking agent can be used. Of these, isocyanate-based crosslinking agents are preferred.
- Other components may be added to the resin composition for constituting the base material.
- a conductive agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, and a solvent can be added.
- the thickness of the substrate is preferably 20 to 200 ⁇ m, more preferably 50 to 150 ⁇ m.
- An adhesive layer is a layer which consists of an adhesive composition, and is provided in the single side
- the pressure-sensitive adhesive composition is not particularly limited as long as it contains a pressure-sensitive adhesive that does not impair the effects of the present invention.
- an emulsion-based adhesive, a solvent-based adhesive, an oligomer-based adhesive, a solid adhesive, and a hot-melt adhesive can be used.
- the pressure-sensitive adhesive layer is particularly preferably made of a pressure-sensitive pressure-sensitive adhesive.
- the type of pressure-sensitive adhesive examples include acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive (natural rubber-based pressure-sensitive adhesive or synthetic rubber-based pressure-sensitive adhesive), silicone-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, and polyamide-based pressure-sensitive adhesive. Agents, epoxy adhesives, vinyl alkyl ether adhesives, and fluorine adhesives. Two or more pressure-sensitive adhesives may be used in combination. Among these, an acrylic pressure-sensitive adhesive is preferable.
- the acrylic pressure-sensitive adhesive is generally a composition containing as a main component a compound obtained by curing an acrylic copolymer [(meth) acrylic acid ester copolymer etc.] as a base polymer with a crosslinking agent. For example, a tackifier, a plasticizer, a filler, and a colorant can be added to the adhesive.
- the pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive on a substrate and causing a crosslinking reaction by heating or ultraviolet irradiation. Further, for example, the pressure-sensitive adhesive can be applied on a release paper or other film, and a pressure-sensitive adhesive layer can be formed by crosslinking reaction by heating or ultraviolet irradiation, and this pressure-sensitive adhesive layer can be bonded to one side or both sides of the substrate. .
- a coating device such as a roll coater, a die coater, or a lip coater can be used. When heating after application, the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
- the pressure-sensitive adhesive sheet of the present invention has the above-described base material and a pressure-sensitive adhesive layer provided on one or both surfaces of the base material.
- a single-sided adhesive tape having an adhesive layer provided on only one side of the substrate may be used, but a double-sided adhesive tape provided on both sides is particularly preferred.
- the thickness of the pressure-sensitive adhesive sheet is preferably 30 to 400 ⁇ m, more preferably 50 to 300 ⁇ m.
- One feature of the pressure-sensitive adhesive sheet of the present invention is that there is no destruction of the sheet upon peeling by stretching. Specifically, it is preferable that the substrate is not broken in the following Pull test.
- Pull test A stainless steel plate is attached to one surface of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other surface, and a 90-degree peel test according to JIS Z 0237 is performed 24 hours later.
- the pressure-sensitive adhesive sheet of the present invention is also characterized by excellent tensile strength and elongation. Specifically, in the following tensile test, it is preferable that the tensile strength is 20 N / mm 2 or more and the elongation is 500% or more.
- tensile test An adhesive sheet having a width of 10 mm and a length of 100 mm is fixed to a tensile tester set at a chuck interval of 30 mm, pulled at a speed of 300 mm / min, tensile strength at break (N / mm 2 ) and elongation (%) Measure.
- part means “part by mass”.
- ⁇ Preparation of acrylic pressure-sensitive adhesive composition In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 70 parts of 2-ethylhexyl acrylate, 4.9 parts of n-butyl acrylate, 10 parts of acrylic acid, 0.1 part of 4-hydroxybutyl acrylate 2 parts of vinyl acetate, 100 parts of ethyl acetate, 0.1 part of n-dodecanethiol as a chain transfer agent and 0.1 part of lauryl peroxide as a radical polymerization initiator were charged. Nitrogen gas was sealed in the reactor, and the polymerization reaction was carried out at 68 ° C. for 3 hours and then at 78 ° C. for 3 hours under a nitrogen gas stream while stirring.
- ⁇ Preparation of polyurethane resin composition A low crystalline linear polyester-based polyurethane resin solution and an isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) were added and stirred with a stirrer until uniform dispersion to obtain a polyurethane resin composition.
- Table 1 shows the type and amount (parts) of the polyurethane resin and the amount (parts) of the crosslinking agent.
- Examples 1-3 and Comparative Examples 1-2> The above polyurethane resin composition is applied to one side of a release paper having a silicone release agent formed on both sides, dried at 50 ° C. for 2 minutes + 100 ° C. for 2 minutes to remove the solvent, and a resin substrate (thickness 70 ⁇ m) Got.
- the above-mentioned acrylic pressure-sensitive adhesive composition was applied to a release paper subjected to a double-sided silicone release treatment and dried to form a pressure-sensitive adhesive layer. And this adhesive layer was bonded together to the base material. Furthermore, the pressure-sensitive adhesive layer was bonded to the opposite surface in the same manner. Thereafter, aging was carried out at 40 ° C. for 3 days to complete the curing reaction of the pressure-sensitive adhesive layer, thereby obtaining a double-sided pressure-sensitive adhesive sheet having a thickness of about 100 ⁇ m (the thickness of each pressure-sensitive adhesive layer was about 15 ⁇ m).
- Softening point of polyurethane resin The softening point of the polyurethane resin was measured according to JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis”.
- Glass transition temperature (Tg) of polyurethane resin Using a viscoelasticity tester for dynamic viscoelasticity measurement, a linear polyester polyurethane resin having a thickness of 0.2 mm is sandwiched between parallel plates of the measurement unit of the tester, and a frequency of 1 Hz is from ⁇ 100 ° C. to 200 ° C. The storage elastic modulus (G ′) and loss elastic modulus (G ′′) up to 0 ° C. were measured. Further, the glass transition temperature (Tg) was determined from Tan ⁇ .
- Weight average molecular weight of polyurethane resin (Mw) The weight average molecular weight (Mw) of the molecular weight in terms of standard polystyrene of the acrylic copolymer was measured by the GPC method using the following measuring apparatus and conditions.
- ⁇ Device LC-2000 series (manufactured by JASCO Corporation) -Column: Shodex KF-806M x 2 and Shodex KF-802 x 1-Eluent: Tetrahydrofuran (THF) ⁇ Flow rate: 1.0 mL / min ⁇ Column temperature: 40 ° C.
- ⁇ Injection volume 100 ⁇ L
- ⁇ Detector Refractometer (RI) Measurement sample: A linear polyester polyurethane resin dissolved in THF to prepare a solution having a linear polyester polyurethane resin concentration of 0.5% by weight, and dust was removed by filtration through a filter.
- Double-sided adhesive sheet is cut into a frame of 0.8mm width and 50x45mm, one release paper is peeled off and bonded to a 2mm thick glass plate, the other release paper is peeled off and a 3mm thick polycarbonate plate Pasted together. Then, using an autoclave, pressure treatment was performed at 23 ° C. and 0.5 MPa for 1 hour. Further, using a SUS plate, the whole weight was adjusted to 250 g, and placed in an environment of ⁇ 20 ° C. for 1 hour or longer. And it dropped on the concrete floor, passing through a pipe
- the double-sided PSA sheet is cut into a frame with a width of 0.8 mm and a size of 40 x 50 mm, one release paper is peeled off and bonded to a 2 mm thick glass plate, and the other release paper is peeled off to remove a 2 mm thick glass.
- the plates were bonded together.
- the sample was reciprocated once by a 2 kg roller. After that, it was submerged in accordance with the IPX7 test method of the waterproof standard IEC “International Electrotechnical Commission” 60529: 2001 [equivalent standard: JIS C 0920: 2003 “special protection grade (IP code) of electrical machinery / equipment”]. It was evaluated whether or not the waterproof property of the standard was satisfied (the item described as “IPX7” in Table 1 satisfies the standard).
- UE1 Low crystalline linear polyester urethane elastomer (manufactured by Sumika Bayer Urethane Co., Ltd., Desmocol (registered trademark) 406)
- UE2 Low crystalline linear polyester urethane elastomer (manufactured by Nippon Polyurethane Industry Co., Ltd., NIPPOLAN (registered trademark) 2304)
- UE3 Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) IB-1700D)
- UE4 Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) LQ-390)
- CR Isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.)
- the adhesive tape of the present invention is a member constituting a portable information terminal device such as a smartphone, a mobile phone, an electronic notebook, a PHS, a tablet PC, a digital camera, a music player, a portable TV, a notebook computer, and a game machine. Useful in gluing or fixing applications. Especially, it is very useful as an adhesive sheet used for fixing battery packs and casings of devices such as smartphones and mobile phones.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
An adhesive sheet that has an adhesive layer on one surface or both surfaces of a substrate and that can be peeled off by being stretched. The adhesive sheet is characterized in that the substrate is obtained using, as a base polymer, a polyurethane resin that has a softening point of 60°C or lower in accordance with JIS K 7196. When the adhesive sheet is peeled off by being stretched, the sheet does not leave a residue (adhesive) behind and does not rupture.
Description
本発明は、接着面内において広範囲の延伸により残留物または破壊無しに剥離可能な片面又は両側感圧性粘着シートに関する。
The present invention relates to a single-sided or double-sided pressure-sensitive adhesive sheet that can be peeled without any residue or breakage by extensive stretching within the adhesive surface.
例えばスマートフォン、携帯電話等の携帯電子機器においては、電池パックと筐体の固定に粘着シートが使用されている。そして電池パックを取り出す際は、粘着シートを引っ張り、その延伸によって剥離させる。このような用途における粘着シートは、剥離の際に残留物（粘着剤）が残らず、シートの破壊が無い等の性能が要求される。
For example, in portable electronic devices such as smartphones and mobile phones, an adhesive sheet is used for fixing the battery pack and the casing. And when taking out a battery pack, an adhesive sheet is pulled and it peels by the extending | stretching. The pressure-sensitive adhesive sheet for such use is required to have performance such as no residue (pressure-sensitive adhesive) remaining at the time of peeling and no destruction of the sheet.
延伸により剥離可能な粘着シートとして、例えば特許文献１には、フィルムを伸長した場合に接着剤層の接着性が消失する特定の接着フィルム片が開示され、特許文献２には、特定のブロックコポリマーから構成される接着剤を感圧接着剤シート片に使用することが開示され、特許文献３には、スチレンブロックコポリマーと酸変性及び／又は酸無水物変性されたエラストマーを含む接着シートストリップが開示され、特許文献４には、特定の裏材層と感圧性接着剤層とを有する接着テープが開示されている。
As an adhesive sheet that can be peeled by stretching, for example, Patent Document 1 discloses a specific adhesive film piece in which the adhesiveness of the adhesive layer disappears when the film is stretched, and Patent Document 2 discloses a specific block copolymer. An adhesive sheet strip comprising a styrene block copolymer and an acid-modified and / or acid-modified elastomer is disclosed in US Pat. Patent Document 4 discloses an adhesive tape having a specific backing layer and a pressure-sensitive adhesive layer.
しかし、従来の延伸により剥離可能な粘着シートは、剥離の際に残留物が残らず、しかもシートの破壊が無い等の性能において更なる改善の余地がある。
However, the conventional pressure-sensitive adhesive sheet that can be peeled by stretching has room for further improvement in performance, such as no residue remaining at the time of peeling, and no destruction of the sheet.
本発明の目的は、延伸による剥離の際に残留物（粘着剤）が残らず、かつシートの破壊も無い粘着シートを提供することにある。
An object of the present invention is to provide a pressure-sensitive adhesive sheet in which a residue (pressure-sensitive adhesive) does not remain at the time of peeling by stretching and the sheet is not broken.
本発明者らは、上記目的を達成すべく鋭意検討した結果、基材のベースポリマーとして特定のウレタン樹脂を用いることが非常に有効であることを見出し、本発明を完成するに至った。
As a result of intensive studies to achieve the above object, the present inventors have found that it is very effective to use a specific urethane resin as the base polymer of the base material, and have completed the present invention.
すなわち本発明は、基材の片面又は両面に粘着剤層を有し、延伸により剥離可能な粘着シートであって、該基材が、ＪＩＳ Ｋ ７１９６に準拠する軟化点が６０℃以下であるポリウレタン樹脂をベースポリマーとして得られることを特徴とする粘着シートである。
That is, the present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side or both sides of a base material and capable of being peeled off by stretching, wherein the base material has a softening point of 60 ° C. or less according to JIS K 7196. A pressure-sensitive adhesive sheet obtained by using a resin as a base polymer.
本発明においては、基材のベースポリマーとして特定のウレタン樹脂を用いるので、適度な柔軟性、伸縮性、引張強度が発現し、その結果延伸による剥離の際にも基材が破壊せず、リワーク性に優れた粘着シートになる。
In the present invention, since a specific urethane resin is used as the base polymer of the base material, appropriate flexibility, stretchability, and tensile strength are exhibited. As a result, the base material does not break even during peeling due to stretching. It becomes a pressure sensitive adhesive sheet.
＜基材＞
本発明に用いる基材は、軟化点が６０℃以下であるポリウレタン樹脂をベースポリマーとして得られることを特徴とする。具体的には、ＪＩＳ Ｋ ７１９６「熱可塑性プラスチックフィルム及びシートの熱機械分析による軟化温度試験方法」に準拠して測定した軟化点が６０℃以下であり、好ましくは３０℃～６０℃である。このように軟化点が比較的低いポリウレタン樹脂を用いることにより基材に適度な柔軟性、伸縮性、引張強度が発現し、その結果延伸による剥離の際にも基材が破壊せず、リワーク性に優れた粘着シートになる。 <Base material>
The base material used in the present invention is characterized in that a polyurethane resin having a softening point of 60 ° C. or lower is obtained as a base polymer. Specifically, the softening point measured in accordance with JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis” is 60 ° C. or less, preferably 30 ° C. to 60 ° C. By using a polyurethane resin with a relatively low softening point in this way, the substrate exhibits appropriate flexibility, stretchability, and tensile strength. As a result, the substrate does not break even during peeling due to stretching, and reworkability It becomes an excellent adhesive sheet.
本発明に用いる基材は、軟化点が６０℃以下であるポリウレタン樹脂をベースポリマーとして得られることを特徴とする。具体的には、ＪＩＳ Ｋ ７１９６「熱可塑性プラスチックフィルム及びシートの熱機械分析による軟化温度試験方法」に準拠して測定した軟化点が６０℃以下であり、好ましくは３０℃～６０℃である。このように軟化点が比較的低いポリウレタン樹脂を用いることにより基材に適度な柔軟性、伸縮性、引張強度が発現し、その結果延伸による剥離の際にも基材が破壊せず、リワーク性に優れた粘着シートになる。 <Base material>
The base material used in the present invention is characterized in that a polyurethane resin having a softening point of 60 ° C. or lower is obtained as a base polymer. Specifically, the softening point measured in accordance with JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis” is 60 ° C. or less, preferably 30 ° C. to 60 ° C. By using a polyurethane resin with a relatively low softening point in this way, the substrate exhibits appropriate flexibility, stretchability, and tensile strength. As a result, the substrate does not break even during peeling due to stretching, and reworkability It becomes an excellent adhesive sheet.
後述する実施例ではＰｕｌｌ試験、リワーク性試験を行った。これら試験は、接着した状態の粘着シートを剥離する際に問題無く簡単に剥離可能とする性能を評価する試験である。本発明は、このような試験において基材が破壊せず、粘着剤の残留物も無いという性能（リワーク性）を有する粘着シートを提供する。例えば、スマートフォンや携帯電話等の情報携帯端末の電池パック等の部品を取り出す際は、粘着シートの一端を引っ張り、その延伸によって剥離させる必要がある。その際、粘着シートを容易に剥離でき、かつ剥離箇所に粘着剤等の残留物が残らないことが望まれる。ここで、基材の柔軟性や伸縮性が高ければ粘着シートの片端を引っ張ることにより接着面内の粘着剤層も広範囲に渡り連続的に均一に引き伸ばされて粘着力が適度に低下し、その結果として残留物（粘着剤）も残らず、簡単に剥離が可能となる。ただし、基材の引張強度が低いと基材が破壊してしまう場合がある。一方、本発明においては特定の物性を有するポリウレタン樹脂を用いるので、それら各問題は生じ難くなるのである。
In the examples described later, a pull test and a reworkability test were performed. These tests are tests for evaluating the performance that allows easy peeling without any problem when peeling the adhesive sheet in the bonded state. This invention provides the adhesive sheet which has the performance (rework property) that a base material does not destroy in such a test and there is no residue of an adhesive. For example, when taking out parts such as a battery pack of an information portable terminal such as a smartphone or a mobile phone, it is necessary to pull one end of the pressure-sensitive adhesive sheet and peel it off by stretching. At that time, it is desirable that the pressure-sensitive adhesive sheet can be easily peeled off and no residue such as a pressure-sensitive adhesive remains at the peeled portion. Here, if the flexibility and stretchability of the substrate is high, the pressure-sensitive adhesive layer within the adhesive surface is stretched uniformly and uniformly over a wide range by pulling one end of the pressure-sensitive adhesive sheet, and the adhesive strength is moderately reduced. As a result, no residue (adhesive) remains, and peeling can be easily performed. However, if the tensile strength of the substrate is low, the substrate may be destroyed. On the other hand, since a polyurethane resin having specific physical properties is used in the present invention, these problems are less likely to occur.
ポリウレタン樹脂のガラス転移温度（Ｔｇ）は、好ましくは－３０℃以上、より好まし－３０℃～－１０℃である。このようにＴｇが比較的高いポリウレタン樹脂を用いることにより柔軟性や伸縮性が高い基材であっても強度はあまり低下せず、その結果延伸による剥離の際にも基材が破壊せず、リワーク性に優れた粘着シートになる。
The glass transition temperature (Tg) of the polyurethane resin is preferably −30 ° C. or higher, more preferably −30 ° C. to −10 ° C. Thus, by using a polyurethane resin having a relatively high Tg, the strength does not decrease so much even if the base material has high flexibility and stretchability. As a result, the base material does not break even when peeled by stretching, An adhesive sheet with excellent reworkability.
ポリウレタン樹脂の重量平均分子量（Ｍｗ）は、好ましくは１００,０００～３００,０００、より好ましくは１００，０００～２００，０００である。このようにＭｗが比較的高いポリウレタン樹脂を用いることにより柔軟性や伸縮性が高い基材であっても強度はあまり低下せず、その結果延伸による剥離の際にも基材が破壊せず、リワーク性に優れた粘着シートになる。
The weight average molecular weight (Mw) of the polyurethane resin is preferably 100,000 to 300,000, more preferably 100,000 to 200,000. Thus, the strength does not decrease so much even if the base material has a high flexibility and stretchability by using a polyurethane resin having a relatively high Mw, and as a result, the base material does not break even when peeling by stretching, An adhesive sheet with excellent reworkability.
ポリウレタン樹脂は、通常、ポリオールと多官能イソシアネートの重合体であり、ポリオール単量体単位からなるソフトセグメントと、多官能イソシアネート化合物や低分子グリコール単量体単位からなるハードセグメントとを含む樹脂である。
The polyurethane resin is usually a polymer of a polyol and a polyfunctional isocyanate, and is a resin containing a soft segment composed of a polyol monomer unit and a hard segment composed of a polyfunctional isocyanate compound or a low molecular glycol monomer unit. .
ポリウレタン樹脂に用いるポリオールは、水酸基を２個以上有する化合物である。ポリオールの水酸基数は、好ましくは２～３であり、より好ましくは２である。ポリオールとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ひまし油系ポリオールを使用できる。２種以上のポリオールを併用しても良い。
The polyol used for the polyurethane resin is a compound having two or more hydroxyl groups. The number of hydroxyl groups in the polyol is preferably 2 to 3, more preferably 2. As the polyol, for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, or castor oil-based polyol can be used. Two or more polyols may be used in combination.
ポリエステルポリオールは、例えば、ポリオール成分と酸成分とのエステル化反応によって得られる。ポリオール成分の具体例としては、エチレングリコール、ジエチレングリコール、１,３－ブタンジオール、１,４－ブタンジオール、ネオペンチルグリコール、３－メチル－１,５－ペンタンジオール、２－ブチル－２－エチル－１,３－プロパンジオール、２,４－ジエチル－１,５－ペンタンジオール、１,２－ヘキサンジオール、１,６－ヘキサンジオール、１,８－オクタンジオール、１,９－ノナンジオール、２－メチル－１,８－オクタンジオール、１,８－デカンジオール、オクタデカンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ヘキサントリオール、ポリプロピレングリコールが挙げられる。酸成分の具体例としては、コハク酸、メチルコハク酸、アジピン酸、ピメリック酸、アゼライン酸、セバシン酸、１,１２－ドデカン二酸、１,１４－テトラデカン二酸、ダイマー酸、２－メチル－１,４－シクロヘキサンジカルボン酸、２－エチル－１,４－シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、イソフタル酸、テレフタル酸、１,４－ナフタレンジカルボン酸、４,４'－ビフェエルジカルボン酸、及びこれらの酸無水物が挙げられる。
Polyester polyol is obtained, for example, by an esterification reaction between a polyol component and an acid component. Specific examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Examples include methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, and polypropylene glycol. Specific examples of the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1 , 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid Examples include acids and acid anhydrides thereof.
ポリエーテルポリオールは、例えば、水、低分子ポリオール（例えばプロピレングリコール、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール）、ビスフェノール類（例えばビスフェノールＡ）又はジヒドロキシベンゼン（例えばカテコール、レゾルシン、ハイドロキノン）を開始剤として、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等のアルキレンオキサイドを付加重合させて得られる。具体例としては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールが挙げられる。
Polyether polyols start with, for example, water, low molecular weight polyols (eg propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol), bisphenols (eg bisphenol A) or dihydroxybenzenes (eg catechol, resorcin, hydroquinone) As an agent, it can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
ポリカプロラクトンポリオールの具体例としては、ε－カプロラクトン、σ－バレーロラクトン等の環状エステルモノマーの開環重合体が挙げられる。
Specific examples of the polycaprolactone polyol include ring-opening polymers of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.
ポリカーボネートポリオール具体例としては、上記各ポリオール成分とホスゲンとを重縮合反応させて得られるポリカーボネートポリオール；上記各ポリオール成分と、炭酸ジメチル、炭酸ジエチル、炭酸ジプロビル、炭酸ジイソプロピル、炭酸ジブチル、エチルブチル炭酸、エチレンカーボネート、プロピレンカーボネート、炭酸ジフェニル、炭酸ジベンジル等の炭酸ジエステル類とをエステル交換縮合させて得られるポリカーボネートポリオール；上記各ポリオール成分を２種以上併用して得られる共重合ポリカーボネートポリオール；上記各ポリカーボネートポリオールとカルボキシル基含有化合物とをエステル化反応させて得られるポリカーボネートポリオール；上記各ポリカーボネートポリオールとヒドロキシル基含有化合物とをエーテル化反応させて得られるポリカーボネートポリオール；上記各ポリカーボネートポリオールとエステル化合物とをエステル交換反応させて得られるポリカーボネートポリオール；上記各ポリカーボネートポリオールとヒドロキシル基含有化合物とをエステル交換反応させて得られるポリカーボネートポリオール；上記各ポリカーボネートポリオールとジカルボン酸化合物とを重縮合反応させて得られるポリエステル系ポリカーボネートポリオール；上記各ポリカーボネートポリオールとアルキレンオキサイドとを共重合させて得られる共重合ポリエーテル系ポリカーボネートポリオール；が挙げられる。
Specific examples of the polycarbonate polyol include polycarbonate polyols obtained by polycondensation reaction of each of the above polyol components and phosgene; each of the above polyol components, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene Polycarbonate polyol obtained by transesterification condensation with carbonic acid diesters such as carbonate, propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymer polycarbonate polyol obtained by using two or more of each of the above polyol components; A polycarbonate polyol obtained by an esterification reaction with a carboxyl group-containing compound; each of the above polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate polyol obtained by etherification reaction; polycarbonate polyol obtained by transesterification of each of the above polycarbonate polyol and ester compound; polycarbonate polyol obtained by transesterification of each of the above polycarbonate polyol and hydroxyl group-containing compound; And polyester polycarbonate polyols obtained by polycondensation reaction of the above polycarbonate polyols and dicarboxylic acid compounds; copolymer polyether polycarbonate polyols obtained by copolymerization of the above polycarbonate polyols and alkylene oxides.
ひまし油系ポリオールは、例えば、ひまし油脂肪酸と上記各ポリオール成分（例えばポリプロピレングリコール）とを反応させて得られる。
Castor oil-based polyol is obtained, for example, by reacting castor oil fatty acid with each of the above polyol components (for example, polypropylene glycol).
ポリウレタン樹脂に用いる多官能イソシアネート化合物としては、例えば、多官能脂肪族系イソシアネート化合物、多官能脂環族系イソシアネート化合物、多官能芳香族系イソシアネート化合物を使用できる。また、これら化合物のトリメチロールプロパンアダクト体、水と反応したビュウレット体、イソシアヌレート環を有する３量体も使用できる。２種以上の多官能イソシアネート化合物を併用しても良い。
As the polyfunctional isocyanate compound used in the polyurethane resin, for example, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, or a polyfunctional aromatic isocyanate compound can be used. Trimethylolpropane adducts of these compounds, burettes reacted with water, and trimers having an isocyanurate ring can also be used. Two or more polyfunctional isocyanate compounds may be used in combination.
多官能芳香族系ジイソシアネート化合物の具体例としては、フェニレンジイソシアネート、２,４－トリレンジイソソアネート、２,６－トリレンジイソシアネート、２,２'一ジフェニルメタンジイソシアネート、４,４'－ジフェニルメタンジイソシアネート、４,４'－トルイジンジイソシアネート、４,４'－ジフェニルエーテルジイソシアネート、４,４'－ジフェニルジイソシアネート、１,５－ナフタレンジイソシアネート、キシリレンジイソシアネートが挙げられる。
Specific examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, Examples include 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
ポリウレタン樹脂は、以上説明したポリオールと多官能イソシアネート化合物を含有する組成物を硬化させて得られる。特に、低結晶性の線状ポリエステル系ポリウレタン樹脂が好ましく、ヘキサンジオールコポリエステル系ポリウレタン樹脂、ポリテトラメチレングリコール系ポリウレタン樹脂がより好ましい。
The polyurethane resin is obtained by curing the composition containing the polyol and the polyfunctional isocyanate compound described above. In particular, a low crystalline linear polyester polyurethane resin is preferable, and a hexanediol copolyester polyurethane resin and a polytetramethylene glycol polyurethane resin are more preferable.
ポリウレタン樹脂の市販品としては、例えば、住化バイエルウレタン社製のデスモコール（登録商標）、日本ポリウレタン工業社製のニッポラン（登録商標）等がある。低結晶性は、具体的にはＪＩＳ Ｋ ６２５３「ゴム硬度規格」に準じて、膜厚６ｍｍの樹脂試験片を作製し１００℃×３０分間で試験片を融解させて２３±２℃、相対湿度５０±５％の環境下に放置してから、樹脂の硬度がショアＡ９０になるまでの時間を測定することにより判定できる。具体的には、ショアＡ９０になるまでの時間が７２時間以上の樹脂を低結晶性の樹脂と言うことができる。
Examples of commercially available polyurethane resins include Desmocol (Registered Trademark) manufactured by Sumika Bayer Urethane Co., Ltd., and Nippon Polan (Registered Trademark) manufactured by Nippon Polyurethane Industry Co., Ltd. Specifically, according to JIS K 6253 “Rubber Hardness Standard”, the low crystallinity is obtained by preparing a resin test piece having a thickness of 6 mm and melting the test piece at 100 ° C. for 30 minutes, 23 ± 2 ° C., relative humidity This can be determined by measuring the time from when the resin is left in an environment of 50 ± 5% until the hardness of the resin reaches Shore A90. Specifically, a resin having a time period of 72 hours or longer until Shore A 90 is reached can be referred to as a low crystalline resin.
さらに本発明においては、ベースポリマーの物性向上の観点から、架橋剤を使用することが好ましい。架橋剤としては、例えば、金属キレート系、金属アルコキシド系、エポキシ系、イソシアネート系、アジリジン系、多官能アクリレート、カルボジイミド系、オキサゾリン系、メラミン系の架橋剤を使用できる。中でも、イソシアネート系架橋剤が好ましい。
Furthermore, in the present invention, it is preferable to use a crosslinking agent from the viewpoint of improving the physical properties of the base polymer. As the crosslinking agent, for example, a metal chelate-based, metal alkoxide-based, epoxy-based, isocyanate-based, aziridine-based, polyfunctional acrylate, carbodiimide-based, oxazoline-based, or melamine-based crosslinking agent can be used. Of these, isocyanate-based crosslinking agents are preferred.
基材を構成する為の樹脂組成物には他の成分を添加しても良い。具体的には、例えば、触媒、他の樹脂成分、発泡剤、粘着付与剤、無機充填剤、有機充填剤、金属粉、顔料、箔状物、軟化剤、可塑剤、老化防止剤、放熱剤、導電剤、酸化防止剤、紫外線吸収剤、光安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤を添加できる。
Other components may be added to the resin composition for constituting the base material. Specifically, for example, catalysts, other resin components, foaming agents, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, anti-aging agents, heat dissipation agents A conductive agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, and a solvent can be added.
基材の厚さは、好ましくは２０～２００μｍ、より好ましくは５０～１５０μｍである。
The thickness of the substrate is preferably 20 to 200 μm, more preferably 50 to 150 μm.
＜粘着剤層＞
粘着剤層は、粘着剤組成物からなる層であり、基材の片面又は両面に設けられる。粘着剤組成物は、本発明の効果を損なわない粘着剤を含む組成物であれば良く、特に限定されない。例えば、エマルジョン系粘着剤、溶剤系粘着剤、オリゴマー系粘着剤、固形粘着剤、ホットメルト型粘着剤を使用できる。粘着剤層は、特に感圧性粘着剤からなるものであることが好ましい。 <Adhesive layer>
An adhesive layer is a layer which consists of an adhesive composition, and is provided in the single side | surface or both surfaces of a base material. The pressure-sensitive adhesive composition is not particularly limited as long as it contains a pressure-sensitive adhesive that does not impair the effects of the present invention. For example, an emulsion-based adhesive, a solvent-based adhesive, an oligomer-based adhesive, a solid adhesive, and a hot-melt adhesive can be used. The pressure-sensitive adhesive layer is particularly preferably made of a pressure-sensitive pressure-sensitive adhesive.
粘着剤層は、粘着剤組成物からなる層であり、基材の片面又は両面に設けられる。粘着剤組成物は、本発明の効果を損なわない粘着剤を含む組成物であれば良く、特に限定されない。例えば、エマルジョン系粘着剤、溶剤系粘着剤、オリゴマー系粘着剤、固形粘着剤、ホットメルト型粘着剤を使用できる。粘着剤層は、特に感圧性粘着剤からなるものであることが好ましい。 <Adhesive layer>
An adhesive layer is a layer which consists of an adhesive composition, and is provided in the single side | surface or both surfaces of a base material. The pressure-sensitive adhesive composition is not particularly limited as long as it contains a pressure-sensitive adhesive that does not impair the effects of the present invention. For example, an emulsion-based adhesive, a solvent-based adhesive, an oligomer-based adhesive, a solid adhesive, and a hot-melt adhesive can be used. The pressure-sensitive adhesive layer is particularly preferably made of a pressure-sensitive pressure-sensitive adhesive.
粘着剤の種類としては、例えば、アクリル系粘着剤、ゴム系粘着剤（天然ゴム系粘着剤又は合成ゴム系粘着剤）、シリコーン系粘着剤、ポリエステル系粘着剤、ウレタン系粘着剤、ポリアミド系粘着剤、エポキシ系粘着剤、ビニルアルキルエーテル系粘着剤、フッ素系粘着剤が挙げられる。２種以上の粘着剤を併用しても良い。中でも、アクリル系粘着剤が好ましい。アクリル系粘着剤は、一般に、ベースポリマーであるアクリル系共重合体［（メタ）アクリル酸エステル共重合体など］を架橋剤で硬化させて得られる化合物を主成分として含む組成物である。粘着剤には、例えば、粘着付与剤、可塑剤、充填剤、着色剤を添加できる。
Examples of the type of pressure-sensitive adhesive include acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive (natural rubber-based pressure-sensitive adhesive or synthetic rubber-based pressure-sensitive adhesive), silicone-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, and polyamide-based pressure-sensitive adhesive. Agents, epoxy adhesives, vinyl alkyl ether adhesives, and fluorine adhesives. Two or more pressure-sensitive adhesives may be used in combination. Among these, an acrylic pressure-sensitive adhesive is preferable. The acrylic pressure-sensitive adhesive is generally a composition containing as a main component a compound obtained by curing an acrylic copolymer [(meth) acrylic acid ester copolymer etc.] as a base polymer with a crosslinking agent. For example, a tackifier, a plasticizer, a filler, and a colorant can be added to the adhesive.
粘着剤層は、例えば、粘着剤を基材上に塗布し、加熱又は紫外線照射により架橋反応させて形成できる。また例えば、粘着剤を離型紙又はその他のフィルム上に塗布し、加熱又は紫外線照射により架橋反応させて粘着剤層を形成し、この粘着剤層を基材の片面又は両面に貼り合せることもできる。粘着剤の塗布には、例えば、ロールコーター、ダイコーター、リップコーター等の塗布装置を使用できる。塗布後に加熱する場合は、加熱による架橋反応と共に粘着剤組成物中の溶剤も除去できる。
＜粘着シート＞ The pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive on a substrate and causing a crosslinking reaction by heating or ultraviolet irradiation. Further, for example, the pressure-sensitive adhesive can be applied on a release paper or other film, and a pressure-sensitive adhesive layer can be formed by crosslinking reaction by heating or ultraviolet irradiation, and this pressure-sensitive adhesive layer can be bonded to one side or both sides of the substrate. . For the application of the pressure-sensitive adhesive, for example, a coating device such as a roll coater, a die coater, or a lip coater can be used. When heating after application, the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
<Adhesive sheet>
＜粘着シート＞ The pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive on a substrate and causing a crosslinking reaction by heating or ultraviolet irradiation. Further, for example, the pressure-sensitive adhesive can be applied on a release paper or other film, and a pressure-sensitive adhesive layer can be formed by crosslinking reaction by heating or ultraviolet irradiation, and this pressure-sensitive adhesive layer can be bonded to one side or both sides of the substrate. . For the application of the pressure-sensitive adhesive, for example, a coating device such as a roll coater, a die coater, or a lip coater can be used. When heating after application, the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
<Adhesive sheet>
本発明の粘着シートは、以上説明した基材と、この基材の片面又は両面に設けられた粘着剤層を有する。粘着剤層を基材の片面のみに設けた片面粘着テープでも良いが、両面に設けた両面粘着テープが特に好ましい。粘着シートの厚さは、好ましくは３０～４００μｍ、より好ましくは５０～３００μｍである。
The pressure-sensitive adhesive sheet of the present invention has the above-described base material and a pressure-sensitive adhesive layer provided on one or both surfaces of the base material. A single-sided adhesive tape having an adhesive layer provided on only one side of the substrate may be used, but a double-sided adhesive tape provided on both sides is particularly preferred. The thickness of the pressure-sensitive adhesive sheet is preferably 30 to 400 μm, more preferably 50 to 300 μm.
本発明の粘着シートは、延伸による剥離の際にシートの破壊が無いことが特徴点の一つである。具体的には、以下のＰｕｌｌ試験において基材の破壊が無いことが好ましい。
［Ｐｕｌｌ試験］
幅１０ｍｍ、長さ４５ｍｍのサイズの粘着シートの一方の面にステンレス板、他方の面にポリカーボネート板を貼着し、２４時間後にＪＩＳ Ｚ ０２３７に準拠する９０度剥離試験を行う。 One feature of the pressure-sensitive adhesive sheet of the present invention is that there is no destruction of the sheet upon peeling by stretching. Specifically, it is preferable that the substrate is not broken in the following Pull test.
[Pull test]
A stainless steel plate is attached to one surface of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other surface, and a 90-degree peel test according to JIS Z 0237 is performed 24 hours later.
［Ｐｕｌｌ試験］
幅１０ｍｍ、長さ４５ｍｍのサイズの粘着シートの一方の面にステンレス板、他方の面にポリカーボネート板を貼着し、２４時間後にＪＩＳ Ｚ ０２３７に準拠する９０度剥離試験を行う。 One feature of the pressure-sensitive adhesive sheet of the present invention is that there is no destruction of the sheet upon peeling by stretching. Specifically, it is preferable that the substrate is not broken in the following Pull test.
[Pull test]
A stainless steel plate is attached to one surface of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other surface, and a 90-degree peel test according to JIS Z 0237 is performed 24 hours later.
本発明の粘着シートは、引張強度や伸びに優れていることも特徴点の一つである。具体的には、以下の引張試験において、引張強度が２０Ｎ／ｍｍ２以上であり、伸びが５００％以上であることが好ましい。
［引張試験］
幅１０ｍｍ、長さ１００ｍｍのサイズの粘着シートを、チャック間隔３０ｍｍに設定した引っ張り試験機に固定し、３００ｍｍ／分の速度で引張り、破断時の引張強度（Ｎ／ｍｍ２）と伸び（％）を測定する。 The pressure-sensitive adhesive sheet of the present invention is also characterized by excellent tensile strength and elongation. Specifically, in the following tensile test, it is preferable that the tensile strength is 20 N / mm 2 or more and the elongation is 500% or more.
[Tensile test]
An adhesive sheet having a width of 10 mm and a length of 100 mm is fixed to a tensile tester set at a chuck interval of 30 mm, pulled at a speed of 300 mm / min, tensile strength at break (N / mm 2 ) and elongation (%) Measure.
［引張試験］
幅１０ｍｍ、長さ１００ｍｍのサイズの粘着シートを、チャック間隔３０ｍｍに設定した引っ張り試験機に固定し、３００ｍｍ／分の速度で引張り、破断時の引張強度（Ｎ／ｍｍ２）と伸び（％）を測定する。 The pressure-sensitive adhesive sheet of the present invention is also characterized by excellent tensile strength and elongation. Specifically, in the following tensile test, it is preferable that the tensile strength is 20 N / mm 2 or more and the elongation is 500% or more.
[Tensile test]
An adhesive sheet having a width of 10 mm and a length of 100 mm is fixed to a tensile tester set at a chuck interval of 30 mm, pulled at a speed of 300 mm / min, tensile strength at break (N / mm 2 ) and elongation (%) Measure.
以下、実施例により本発明をさらに詳細に説明する。以下の記載において「部」は「質量部」を意味する。
Hereinafter, the present invention will be described in more detail with reference to examples. In the following description, “part” means “part by mass”.
＜アクリル系粘着剤組成物の調製＞
撹拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応装置に、２－エチルヘキシルアクリレート７０部、ｎ－ブチルアクリレート４.９部、アクリル酸１０部、４－ヒドロキシブチルアクリレート０.１部酢酸ビニル２部、酢酸エチル１００部、連鎖移動剤としてｎ－ドデカンチオール０.１部及びラジカル重合開始剤としてラウリルパーオキサイド０.１部を仕込んだ。反応装置内に窒素ガスを封入し、撹拌しながら窒素ガス気流下に６８℃で３時間、次いで７８℃で３時間重合反応させた。 <Preparation of acrylic pressure-sensitive adhesive composition>
In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 70 parts of 2-ethylhexyl acrylate, 4.9 parts of n-butyl acrylate, 10 parts of acrylic acid, 0.1 part of 4-hydroxybutyl acrylate 2 parts of vinyl acetate, 100 parts of ethyl acetate, 0.1 part of n-dodecanethiol as a chain transfer agent and 0.1 part of lauryl peroxide as a radical polymerization initiator were charged. Nitrogen gas was sealed in the reactor, and the polymerization reaction was carried out at 68 ° C. for 3 hours and then at 78 ° C. for 3 hours under a nitrogen gas stream while stirring.
撹拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応装置に、２－エチルヘキシルアクリレート７０部、ｎ－ブチルアクリレート４.９部、アクリル酸１０部、４－ヒドロキシブチルアクリレート０.１部酢酸ビニル２部、酢酸エチル１００部、連鎖移動剤としてｎ－ドデカンチオール０.１部及びラジカル重合開始剤としてラウリルパーオキサイド０.１部を仕込んだ。反応装置内に窒素ガスを封入し、撹拌しながら窒素ガス気流下に６８℃で３時間、次いで７８℃で３時間重合反応させた。 <Preparation of acrylic pressure-sensitive adhesive composition>
In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 70 parts of 2-ethylhexyl acrylate, 4.9 parts of n-butyl acrylate, 10 parts of acrylic acid, 0.1 part of 4-hydroxybutyl acrylate 2 parts of vinyl acetate, 100 parts of ethyl acetate, 0.1 part of n-dodecanethiol as a chain transfer agent and 0.1 part of lauryl peroxide as a radical polymerization initiator were charged. Nitrogen gas was sealed in the reactor, and the polymerization reaction was carried out at 68 ° C. for 3 hours and then at 78 ° C. for 3 hours under a nitrogen gas stream while stirring.
その後、室温まで冷却して酢酸エチルを添加した。これにより、固形分濃度３０％、理論Ｔｇ－６２.３℃、重量平均分子量１１０万のアクリル系共重合体を得た。次いで、このアクリル系共重合体１００部にイソシアネート系架橋剤（日本ポリウレタン工業社製、コロネート（登録商標）Ｌ）０.０７部及び適量の有機溶剤を加えて、撹拌機で均一になるまで撹拌し、アクリル系粘着剤組成物を得た
Then, it was cooled to room temperature and ethyl acetate was added. As a result, an acrylic copolymer having a solid content concentration of 30%, a theoretical Tg of 62.3 ° C., and a weight average molecular weight of 1.1 million was obtained. Next, 0.07 part of an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate (registered trademark) L) and an appropriate amount of an organic solvent are added to 100 parts of this acrylic copolymer and stirred with a stirrer until uniform. And obtained an acrylic pressure-sensitive adhesive composition
＜ポリウレタン樹脂組成物の調製＞
低結晶性の線状ポリエステル系ポリウレタン樹脂溶液及びイソシアネート系架橋剤（日本ポリウレタン社製、商品名コロネートＬ）を加えて、撹拌機で均一分散になるまで撹拌し、ポリウレタン樹脂組成物を得た。ポリウレタン樹脂の種類及び量（部）、架橋剤の量（部）は表１に示す。 <Preparation of polyurethane resin composition>
A low crystalline linear polyester-based polyurethane resin solution and an isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) were added and stirred with a stirrer until uniform dispersion to obtain a polyurethane resin composition. Table 1 shows the type and amount (parts) of the polyurethane resin and the amount (parts) of the crosslinking agent.
低結晶性の線状ポリエステル系ポリウレタン樹脂溶液及びイソシアネート系架橋剤（日本ポリウレタン社製、商品名コロネートＬ）を加えて、撹拌機で均一分散になるまで撹拌し、ポリウレタン樹脂組成物を得た。ポリウレタン樹脂の種類及び量（部）、架橋剤の量（部）は表１に示す。 <Preparation of polyurethane resin composition>
A low crystalline linear polyester-based polyurethane resin solution and an isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) were added and stirred with a stirrer until uniform dispersion to obtain a polyurethane resin composition. Table 1 shows the type and amount (parts) of the polyurethane resin and the amount (parts) of the crosslinking agent.
＜実施例１～３及び比較例１～２＞
上記のポリウレタン樹脂組成物を、両面にシリコーン離型剤を形成した剥離紙の片面に塗布し、５０℃２分間＋１００℃２分間で乾燥して溶媒を除去して樹脂基材（厚さ７０μｍ）を得た。 <Examples 1-3 and Comparative Examples 1-2>
The above polyurethane resin composition is applied to one side of a release paper having a silicone release agent formed on both sides, dried at 50 ° C. for 2 minutes + 100 ° C. for 2 minutes to remove the solvent, and a resin substrate (thickness 70 μm) Got.
上記のポリウレタン樹脂組成物を、両面にシリコーン離型剤を形成した剥離紙の片面に塗布し、５０℃２分間＋１００℃２分間で乾燥して溶媒を除去して樹脂基材（厚さ７０μｍ）を得た。 <Examples 1-3 and Comparative Examples 1-2>
The above polyurethane resin composition is applied to one side of a release paper having a silicone release agent formed on both sides, dried at 50 ° C. for 2 minutes + 100 ° C. for 2 minutes to remove the solvent, and a resin substrate (thickness 70 μm) Got.
両面シリコーン離型処理した剥離紙に、上記のアクリル系粘着剤組成物を塗布・乾燥し、粘着剤層を形成した。そしてこの粘着剤層を基材に貼り合わせた。さらに、反対面にも同じ方法で粘着剤層を貼り合わせた。その後、４０℃で３日間熟成し、粘着剤層の硬化反応を完結させて、厚さ約１００μｍの両面粘着シート（各粘着剤層の厚さ約１５μｍ）を得た。
The above-mentioned acrylic pressure-sensitive adhesive composition was applied to a release paper subjected to a double-sided silicone release treatment and dried to form a pressure-sensitive adhesive layer. And this adhesive layer was bonded together to the base material. Furthermore, the pressure-sensitive adhesive layer was bonded to the opposite surface in the same manner. Thereafter, aging was carried out at 40 ° C. for 3 days to complete the curing reaction of the pressure-sensitive adhesive layer, thereby obtaining a double-sided pressure-sensitive adhesive sheet having a thickness of about 100 μm (the thickness of each pressure-sensitive adhesive layer was about 15 μm).
以上のようにして得た各粘着シートに対して、物性や性能評価は以下の方法に従い行った。結果を表１に示す。
For each pressure-sensitive adhesive sheet obtained as described above, physical properties and performance evaluation were performed according to the following methods. The results are shown in Table 1.
［ポリウレタン樹脂の軟化点］
ＪＩＳ Ｋ ７１９６「熱可塑性プラスチックフィルム及びシートの熱機械分析による軟化温度試験方法」に準拠し、ポリウレタン樹脂の軟化点を測定した。 [Softening point of polyurethane resin]
The softening point of the polyurethane resin was measured according to JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis”.
ＪＩＳ Ｋ ７１９６「熱可塑性プラスチックフィルム及びシートの熱機械分析による軟化温度試験方法」に準拠し、ポリウレタン樹脂の軟化点を測定した。 [Softening point of polyurethane resin]
The softening point of the polyurethane resin was measured according to JIS K 7196 “Testing method for softening temperature of thermoplastic film and sheet by thermomechanical analysis”.
［ポリウレタン樹脂のガラス転移温度（Ｔｇ）］
動的粘弾性測定の為に粘弾性試験機を用いて、厚さ０.２ｍｍの線状ポリエステル系ポリウレタン樹脂を試験機の測定部の平行盤の間に挟み込み、周波数１Ｈｚで－１００℃から２００℃までの貯蔵弾性率（Ｇ'）と損失弾性率（Ｇ''）を測定した。さらにＴａｎδからガラス転移温度（Ｔｇ）を求めた。 [Glass transition temperature (Tg) of polyurethane resin]
Using a viscoelasticity tester for dynamic viscoelasticity measurement, a linear polyester polyurethane resin having a thickness of 0.2 mm is sandwiched between parallel plates of the measurement unit of the tester, and a frequency of 1 Hz is from −100 ° C. to 200 ° C. The storage elastic modulus (G ′) and loss elastic modulus (G ″) up to 0 ° C. were measured. Further, the glass transition temperature (Tg) was determined from Tan δ.
動的粘弾性測定の為に粘弾性試験機を用いて、厚さ０.２ｍｍの線状ポリエステル系ポリウレタン樹脂を試験機の測定部の平行盤の間に挟み込み、周波数１Ｈｚで－１００℃から２００℃までの貯蔵弾性率（Ｇ'）と損失弾性率（Ｇ''）を測定した。さらにＴａｎδからガラス転移温度（Ｔｇ）を求めた。 [Glass transition temperature (Tg) of polyurethane resin]
Using a viscoelasticity tester for dynamic viscoelasticity measurement, a linear polyester polyurethane resin having a thickness of 0.2 mm is sandwiched between parallel plates of the measurement unit of the tester, and a frequency of 1 Hz is from −100 ° C. to 200 ° C. The storage elastic modulus (G ′) and loss elastic modulus (G ″) up to 0 ° C. were measured. Further, the glass transition temperature (Tg) was determined from Tan δ.
［ポリウレタン樹脂の重量平均分子量（Ｍｗ）］
ＧＰＣ法により、アクリル系共重合体の標準ポリスチレン換算の分子量を以下の測定装置及び条件にて重量平均分子量（Ｍｗ）を測定した。
・装置：ＬＣ－２０００シリーズ（日本分光株式会社製）
・カラム：Ｓｈｏｄｅｘ ＫＦ－８０６Ｍ×２本、Ｓｈｏｄｅｘ ＫＦ－８０２×１本
・溶離液：テトラヒドロフラン（ＴＨＦ）
・流速：１.０ｍＬ／分
・カラム温度：４０℃
・注入量：１００μＬ
・検出器：屈折率計（ＲＩ）
・測定サンプル：線状ポリエステル系ポリウレタン樹脂をＴＨＦに溶解させ、線状ポリエステル系ポリウレタン樹脂濃度が０.５重量％の溶液を作製し、フィルターによるろ過でゴミを除去したもの。 [Weight average molecular weight of polyurethane resin (Mw)]
The weight average molecular weight (Mw) of the molecular weight in terms of standard polystyrene of the acrylic copolymer was measured by the GPC method using the following measuring apparatus and conditions.
・ Device: LC-2000 series (manufactured by JASCO Corporation)
-Column: Shodex KF-806M x 2 and Shodex KF-802 x 1-Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min ・ Column temperature: 40 ° C.
・ Injection volume: 100 μL
・ Detector: Refractometer (RI)
Measurement sample: A linear polyester polyurethane resin dissolved in THF to prepare a solution having a linear polyester polyurethane resin concentration of 0.5% by weight, and dust was removed by filtration through a filter.
ＧＰＣ法により、アクリル系共重合体の標準ポリスチレン換算の分子量を以下の測定装置及び条件にて重量平均分子量（Ｍｗ）を測定した。
・装置：ＬＣ－２０００シリーズ（日本分光株式会社製）
・カラム：Ｓｈｏｄｅｘ ＫＦ－８０６Ｍ×２本、Ｓｈｏｄｅｘ ＫＦ－８０２×１本
・溶離液：テトラヒドロフラン（ＴＨＦ）
・流速：１.０ｍＬ／分
・カラム温度：４０℃
・注入量：１００μＬ
・検出器：屈折率計（ＲＩ）
・測定サンプル：線状ポリエステル系ポリウレタン樹脂をＴＨＦに溶解させ、線状ポリエステル系ポリウレタン樹脂濃度が０.５重量％の溶液を作製し、フィルターによるろ過でゴミを除去したもの。 [Weight average molecular weight of polyurethane resin (Mw)]
The weight average molecular weight (Mw) of the molecular weight in terms of standard polystyrene of the acrylic copolymer was measured by the GPC method using the following measuring apparatus and conditions.
・ Device: LC-2000 series (manufactured by JASCO Corporation)
-Column: Shodex KF-806M x 2 and Shodex KF-802 x 1-Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min ・ Column temperature: 40 ° C.
・ Injection volume: 100 μL
・ Detector: Refractometer (RI)
Measurement sample: A linear polyester polyurethane resin dissolved in THF to prepare a solution having a linear polyester polyurethane resin concentration of 0.5% by weight, and dust was removed by filtration through a filter.
［Ｐｕｌｌ試験］
幅１０ｍｍ、長さ４５ｍｍのサイズの粘着シートの一方の面にステンレス板、他方の面にポリカーボネート板を貼着し、２４時間後にＪＩＳ Ｚ ０２３７に準拠する９０度剥離試験を行い、以下の基準で評価した。
「〇」：基材は破壊せず、粘着剤の残留物も無かった。
「×」：基材が破壊した。 [Pull test]
A stainless steel plate is attached to one side of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other side. After 90 hours, a 90-degree peel test in accordance with JIS Z 0237 is performed. evaluated.
“◯”: The base material was not destroyed and there was no adhesive residue.
“X”: The substrate was broken.
幅１０ｍｍ、長さ４５ｍｍのサイズの粘着シートの一方の面にステンレス板、他方の面にポリカーボネート板を貼着し、２４時間後にＪＩＳ Ｚ ０２３７に準拠する９０度剥離試験を行い、以下の基準で評価した。
「〇」：基材は破壊せず、粘着剤の残留物も無かった。
「×」：基材が破壊した。 [Pull test]
A stainless steel plate is attached to one side of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other side. After 90 hours, a 90-degree peel test in accordance with JIS Z 0237 is performed. evaluated.
“◯”: The base material was not destroyed and there was no adhesive residue.
“X”: The substrate was broken.
［細幅加工性］
両面粘着シートを幅５ｍｍ、長さ１２５ｍｍのサイズで１０本に細断した状態を維持したまま（すなわち細断した各々の粘着シートが細断時の隣接した状態を維持したまま）、６５℃、８０％ＲＨの雰囲気下に１日放置した。そして１本毎に１８０度方向に離型紙ごと剥離し、隣接した部分との癒着を目視にて確認し、以下の基準で細幅加工性を評価した。
「〇」：隣接した部分との癒着がほとんど無く、隣接部分を剥すことなく剥離できた。
「×」：隣接した部分に著しい癒着があり、隣接部分が同時に剥れてしまった。 [Narrow width workability]
While maintaining the state that the double-sided PSA sheet is shredded into 10 pieces with a width of 5 mm and a length of 125 mm (that is, each sliced PSA sheet is kept adjacent to the shredded state), 65 ° C., It was left for 1 day in an atmosphere of 80% RH. Then, the release paper was peeled in the direction of 180 degrees for each one, the adhesion with the adjacent portion was visually confirmed, and the narrow width workability was evaluated according to the following criteria.
“◯”: There was almost no adhesion with the adjacent part, and it was able to peel without peeling off the adjacent part.
"X": There was remarkable adhesion in the adjacent part, and the adjacent part was peeled off at the same time.
両面粘着シートを幅５ｍｍ、長さ１２５ｍｍのサイズで１０本に細断した状態を維持したまま（すなわち細断した各々の粘着シートが細断時の隣接した状態を維持したまま）、６５℃、８０％ＲＨの雰囲気下に１日放置した。そして１本毎に１８０度方向に離型紙ごと剥離し、隣接した部分との癒着を目視にて確認し、以下の基準で細幅加工性を評価した。
「〇」：隣接した部分との癒着がほとんど無く、隣接部分を剥すことなく剥離できた。
「×」：隣接した部分に著しい癒着があり、隣接部分が同時に剥れてしまった。 [Narrow width workability]
While maintaining the state that the double-sided PSA sheet is shredded into 10 pieces with a width of 5 mm and a length of 125 mm (that is, each sliced PSA sheet is kept adjacent to the shredded state), 65 ° C., It was left for 1 day in an atmosphere of 80% RH. Then, the release paper was peeled in the direction of 180 degrees for each one, the adhesion with the adjacent portion was visually confirmed, and the narrow width workability was evaluated according to the following criteria.
“◯”: There was almost no adhesion with the adjacent part, and it was able to peel without peeling off the adjacent part.
"X": There was remarkable adhesion in the adjacent part, and the adjacent part was peeled off at the same time.
［リワーク性］
両面粘着シートをステンレス板に貼着し、３０分後に９０度剥離試験を行い、以下の基準で評価した。
「〇」：基材は破壊せず、粘着剤の残留物も無かった。
「×」：基材が破壊した。 [Reworkability]
The double-sided PSA sheet was attached to a stainless steel plate, a 90-degree peel test was performed after 30 minutes, and the following criteria were evaluated.
“◯”: The base material was not destroyed and there was no adhesive residue.
“X”: The substrate was broken.
両面粘着シートをステンレス板に貼着し、３０分後に９０度剥離試験を行い、以下の基準で評価した。
「〇」：基材は破壊せず、粘着剤の残留物も無かった。
「×」：基材が破壊した。 [Reworkability]
The double-sided PSA sheet was attached to a stainless steel plate, a 90-degree peel test was performed after 30 minutes, and the following criteria were evaluated.
“◯”: The base material was not destroyed and there was no adhesive residue.
“X”: The substrate was broken.
［耐荷重性］
両面粘着シートを２５×２５ｍｍのサイズに裁断し、一方の離型紙を剥離した。試験用フック板に両面粘着シートを貼り合せ、次いでもう一方の離型紙を剥離し、ポリカーボネート板に貼り合せた。そしてフックに７００ｇｆの荷重をかけ、８５℃で６０分間保持し、以下の基準で耐荷重性を評価した。
「〇」：６０分間フックは落下しなかった。
「×」：６０分以内にフックが落下した。 [Load resistance]
The double-sided PSA sheet was cut to a size of 25 × 25 mm, and one release paper was peeled off. The double-sided PSA sheet was bonded to the test hook plate, and then the other release paper was peeled off and bonded to the polycarbonate plate. A load of 700 gf was applied to the hook and held at 85 ° C. for 60 minutes, and load resistance was evaluated according to the following criteria.
“◯”: The hook did not fall for 60 minutes.
"X": The hook fell within 60 minutes.
両面粘着シートを２５×２５ｍｍのサイズに裁断し、一方の離型紙を剥離した。試験用フック板に両面粘着シートを貼り合せ、次いでもう一方の離型紙を剥離し、ポリカーボネート板に貼り合せた。そしてフックに７００ｇｆの荷重をかけ、８５℃で６０分間保持し、以下の基準で耐荷重性を評価した。
「〇」：６０分間フックは落下しなかった。
「×」：６０分以内にフックが落下した。 [Load resistance]
The double-sided PSA sheet was cut to a size of 25 × 25 mm, and one release paper was peeled off. The double-sided PSA sheet was bonded to the test hook plate, and then the other release paper was peeled off and bonded to the polycarbonate plate. A load of 700 gf was applied to the hook and held at 85 ° C. for 60 minutes, and load resistance was evaluated according to the following criteria.
“◯”: The hook did not fall for 60 minutes.
"X": The hook fell within 60 minutes.
［耐衝撃性］
両面粘着シートを幅０.８ｍｍで５０×４５ｍｍの枠状に裁断し、一方の離型紙を剥離して２ｍｍ厚のガラス板に貼り合せ、もう一方の剥離紙を剥離して３ｍｍ厚のポリカーボネート板に貼り合せた。そしてオートクレーブを用いて、２３℃、０.５ＭＰａで１時間の加圧処理を行った。さらにＳＵＳ板を用いて全体の重さを２５０ｇになる様に調整し、－２０℃の環境下に１時間以上置いた。そして、１.５ｍの高さから試験板が垂直方向なる様に筒の中を通しながらコンクリート床に落とし、ガラス板が剥れる落下回数を測定した。 [Shock resistance]
Double-sided adhesive sheet is cut into a frame of 0.8mm width and 50x45mm, one release paper is peeled off and bonded to a 2mm thick glass plate, the other release paper is peeled off and a 3mm thick polycarbonate plate Pasted together. Then, using an autoclave, pressure treatment was performed at 23 ° C. and 0.5 MPa for 1 hour. Further, using a SUS plate, the whole weight was adjusted to 250 g, and placed in an environment of −20 ° C. for 1 hour or longer. And it dropped on the concrete floor, passing through a pipe | tube so that a test board might become a perpendicular direction from the height of 1.5 m, and the frequency | count of the fall which a glass plate peels was measured.
両面粘着シートを幅０.８ｍｍで５０×４５ｍｍの枠状に裁断し、一方の離型紙を剥離して２ｍｍ厚のガラス板に貼り合せ、もう一方の剥離紙を剥離して３ｍｍ厚のポリカーボネート板に貼り合せた。そしてオートクレーブを用いて、２３℃、０.５ＭＰａで１時間の加圧処理を行った。さらにＳＵＳ板を用いて全体の重さを２５０ｇになる様に調整し、－２０℃の環境下に１時間以上置いた。そして、１.５ｍの高さから試験板が垂直方向なる様に筒の中を通しながらコンクリート床に落とし、ガラス板が剥れる落下回数を測定した。 [Shock resistance]
Double-sided adhesive sheet is cut into a frame of 0.8mm width and 50x45mm, one release paper is peeled off and bonded to a 2mm thick glass plate, the other release paper is peeled off and a 3mm thick polycarbonate plate Pasted together. Then, using an autoclave, pressure treatment was performed at 23 ° C. and 0.5 MPa for 1 hour. Further, using a SUS plate, the whole weight was adjusted to 250 g, and placed in an environment of −20 ° C. for 1 hour or longer. And it dropped on the concrete floor, passing through a pipe | tube so that a test board might become a perpendicular direction from the height of 1.5 m, and the frequency | count of the fall which a glass plate peels was measured.
［防水性］
両面粘着シートを幅０.８ｍｍで４０×５０ｍｍの枠状に裁断し、一方の離型紙を剥離して２ｍｍ厚のガラス板に貼り合わせ、更にもう一方の離型紙を剥離して２ｍｍ厚のガラス板を貼り合せた。そしてこのサンプルに対し、２ｋｇのローラーを１往復した。その後、防水規格ＩＥＣ「国際電気標準会議」６０５２９：２００１〔同等規格：ＪＩＳ Ｃ ０９２０：２００３「電気機械器具の外郭による保護特級（ＩＰコード）」〕のＩＰＸ７の試験方法に基づき水没させて、ＩＰＸ７の規格の防水性を満たすかどうか評価した（表１中に「ＩＰＸ７」と記載されるものは規格を満たすものである）。 [Waterproof]
The double-sided PSA sheet is cut into a frame with a width of 0.8 mm and a size of 40 x 50 mm, one release paper is peeled off and bonded to a 2 mm thick glass plate, and the other release paper is peeled off to remove a 2 mm thick glass. The plates were bonded together. The sample was reciprocated once by a 2 kg roller. After that, it was submerged in accordance with the IPX7 test method of the waterproof standard IEC “International Electrotechnical Commission” 60529: 2001 [equivalent standard: JIS C 0920: 2003 “special protection grade (IP code) of electrical machinery / equipment”]. It was evaluated whether or not the waterproof property of the standard was satisfied (the item described as “IPX7” in Table 1 satisfies the standard).
両面粘着シートを幅０.８ｍｍで４０×５０ｍｍの枠状に裁断し、一方の離型紙を剥離して２ｍｍ厚のガラス板に貼り合わせ、更にもう一方の離型紙を剥離して２ｍｍ厚のガラス板を貼り合せた。そしてこのサンプルに対し、２ｋｇのローラーを１往復した。その後、防水規格ＩＥＣ「国際電気標準会議」６０５２９：２００１〔同等規格：ＪＩＳ Ｃ ０９２０：２００３「電気機械器具の外郭による保護特級（ＩＰコード）」〕のＩＰＸ７の試験方法に基づき水没させて、ＩＰＸ７の規格の防水性を満たすかどうか評価した（表１中に「ＩＰＸ７」と記載されるものは規格を満たすものである）。 [Waterproof]
The double-sided PSA sheet is cut into a frame with a width of 0.8 mm and a size of 40 x 50 mm, one release paper is peeled off and bonded to a 2 mm thick glass plate, and the other release paper is peeled off to remove a 2 mm thick glass. The plates were bonded together. The sample was reciprocated once by a 2 kg roller. After that, it was submerged in accordance with the IPX7 test method of the waterproof standard IEC “International Electrotechnical Commission” 60529: 2001 [equivalent standard: JIS C 0920: 2003 “special protection grade (IP code) of electrical machinery / equipment”]. It was evaluated whether or not the waterproof property of the standard was satisfied (the item described as “IPX7” in Table 1 satisfies the standard).
［引張強度・伸び］
両面粘着シートを幅１０ｍｍ、長さ１００ｍｍに切り出し、チャック間隔を３０ｍｍに設定した引張試験機に固定し、３００ｍｍ／分の速度で引っ張って、破断時の引張強度（Ｎ／ｍｍ2）と伸び（％）を測定した。 [Tensile strength / elongation]
The double-sided PSA sheet was cut out to a width of 10 mm and a length of 100 mm, fixed to a tensile tester with a chuck interval set to 30 mm, and pulled at a speed of 300 mm / min to obtain a tensile strength (N / mm 2 ) and elongation at break (N %).
両面粘着シートを幅１０ｍｍ、長さ１００ｍｍに切り出し、チャック間隔を３０ｍｍに設定した引張試験機に固定し、３００ｍｍ／分の速度で引っ張って、破断時の引張強度（Ｎ／ｍｍ2）と伸び（％）を測定した。 [Tensile strength / elongation]
The double-sided PSA sheet was cut out to a width of 10 mm and a length of 100 mm, fixed to a tensile tester with a chuck interval set to 30 mm, and pulled at a speed of 300 mm / min to obtain a tensile strength (N / mm 2 ) and elongation at break (N %).
表１中の略号は以下の化合物を示す。
［ＵＥ１］：低結晶性の線状ポリエステル系ウレタンエラストマー（住化バイエルウレタン社製、デスモコール（登録商標）４０６）
［ＵＥ２］：低結晶性の線状ポリエステル系ウレタンエラストマー（日本ポリウレタン工業社製、ニッポラン（登録商標）２３０４）
［ＵＥ３］：低結晶性の線状ポリエステル系ウレタンエラストマー（三洋化成工業社製、サンプレン（登録商標）ＩＢ－１７００Ｄ）
［ＵＥ４］：低結晶性の線状ポリエステル系ウレタンエラストマー（三洋化成工業社製、サンプレン（登録商標）ＬＱ－３９０）
「ＣＲ」：イソシアネート系架橋剤（日本ポリウレタン社製、商品名コロネートＬ） The abbreviations in Table 1 indicate the following compounds.
[UE1]: Low crystalline linear polyester urethane elastomer (manufactured by Sumika Bayer Urethane Co., Ltd., Desmocol (registered trademark) 406)
[UE2]: Low crystalline linear polyester urethane elastomer (manufactured by Nippon Polyurethane Industry Co., Ltd., NIPPOLAN (registered trademark) 2304)
[UE3]: Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) IB-1700D)
[UE4]: Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) LQ-390)
“CR”: Isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.)
［ＵＥ１］：低結晶性の線状ポリエステル系ウレタンエラストマー（住化バイエルウレタン社製、デスモコール（登録商標）４０６）
［ＵＥ２］：低結晶性の線状ポリエステル系ウレタンエラストマー（日本ポリウレタン工業社製、ニッポラン（登録商標）２３０４）
［ＵＥ３］：低結晶性の線状ポリエステル系ウレタンエラストマー（三洋化成工業社製、サンプレン（登録商標）ＩＢ－１７００Ｄ）
［ＵＥ４］：低結晶性の線状ポリエステル系ウレタンエラストマー（三洋化成工業社製、サンプレン（登録商標）ＬＱ－３９０）
「ＣＲ」：イソシアネート系架橋剤（日本ポリウレタン社製、商品名コロネートＬ） The abbreviations in Table 1 indicate the following compounds.
[UE1]: Low crystalline linear polyester urethane elastomer (manufactured by Sumika Bayer Urethane Co., Ltd., Desmocol (registered trademark) 406)
[UE2]: Low crystalline linear polyester urethane elastomer (manufactured by Nippon Polyurethane Industry Co., Ltd., NIPPOLAN (registered trademark) 2304)
[UE3]: Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) IB-1700D)
[UE4]: Low crystalline linear polyester urethane elastomer (manufactured by Sanyo Chemical Industries, Samprene (registered trademark) LQ-390)
“CR”: Isocyanate-based crosslinking agent (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.)
＜評価＞
表１に示す結果から明らかなように、実施例１及び２の粘着シートは各特性が優れていた。一方、比較例１及び２の粘着シートは、Ｐｕｌｌ試験では基材が破壊し、リワーク性及び／又は引張強度が劣っていた。 <Evaluation>
As is clear from the results shown in Table 1, the pressure-sensitive adhesive sheets of Examples 1 and 2 were excellent in each characteristic. On the other hand, in the pressure-sensitive adhesive sheets of Comparative Examples 1 and 2, the base material was broken in the Pull test, and the reworkability and / or the tensile strength was inferior.
表１に示す結果から明らかなように、実施例１及び２の粘着シートは各特性が優れていた。一方、比較例１及び２の粘着シートは、Ｐｕｌｌ試験では基材が破壊し、リワーク性及び／又は引張強度が劣っていた。 <Evaluation>
As is clear from the results shown in Table 1, the pressure-sensitive adhesive sheets of Examples 1 and 2 were excellent in each characteristic. On the other hand, in the pressure-sensitive adhesive sheets of Comparative Examples 1 and 2, the base material was broken in the Pull test, and the reworkability and / or the tensile strength was inferior.
本発明の粘着テープは優れたリワーク性を有するので、部品交換作業が容易になる。したがって、本発明の粘着テープは、例えばスマートフォン、携帯電話、電子手帳、ＰＨＳ、タブレットＰＣ、デジタルカメラ、音楽プレーヤー、携帯型テレビ、ノート型パソコン、ゲーム機等の携帯情報端末機器を構成する部材の接着又は固定の用途において有用である。中でも、スマートフォンや携帯電話等の機器の電池パックと筐体の固定に用いる粘着シートとして非常に有用である。
Since the pressure-sensitive adhesive tape of the present invention has excellent reworkability, it is easy to replace parts. Therefore, the adhesive tape of the present invention is a member constituting a portable information terminal device such as a smartphone, a mobile phone, an electronic notebook, a PHS, a tablet PC, a digital camera, a music player, a portable TV, a notebook computer, and a game machine. Useful in gluing or fixing applications. Especially, it is very useful as an adhesive sheet used for fixing battery packs and casings of devices such as smartphones and mobile phones.
Claims (9)
- 基材の片面又は両面に粘着剤層を有し、延伸により剥離可能な粘着シートであって、該基材が、ＪＩＳ Ｋ ７１９６に準拠する軟化点が６０℃以下であるポリウレタン樹脂をベースポリマーとして得られることを特徴とする粘着シート。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side or both sides of a base material and capable of being peeled off by stretching, wherein the base material is based on a polyurethane resin having a softening point of 60 ° C. or less in accordance with JIS K 7196 A pressure-sensitive adhesive sheet obtained.
- ポリウレタン樹脂が、低結晶性の線状ポリエステル系ポリウレタン樹脂である請求項１記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the polyurethane resin is a low-crystalline linear polyester polyurethane resin.
- 基材の両面に粘着剤層を有する請求項１記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, which has a pressure-sensitive adhesive layer on both surfaces of the substrate.
- 以下のＰｕｌｌ試験において基材の破壊が無い請求項３記載の粘着シート。
［Ｐｕｌｌ試験］
幅１０ｍｍ、長さ４５ｍｍのサイズの粘着シートの一方の面にステンレス板、他方の面にポリカーボネート板を貼着し、２４時間後にＪＩＳ Ｚ ０２３７に準拠する９０度剥離試験を行う。 The pressure-sensitive adhesive sheet according to claim 3, wherein the base material is not broken in the following Pull test.
[Pull test]
A stainless steel plate is attached to one surface of a pressure-sensitive adhesive sheet having a width of 10 mm and a length of 45 mm, and a polycarbonate plate is attached to the other surface, and a 90-degree peel test according to JIS Z 0237 is performed 24 hours later. - 基材のガラス転移温度（Ｔｇ）が－３０℃以上である請求項１記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the glass transition temperature (Tg) of the substrate is -30 ° C or higher.
- ポリウレタン樹脂の重量平均分子量が１００,０００～３００,０００である請求項１記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the polyurethane resin has a weight average molecular weight of 100,000 to 300,000.
- 粘着剤層が感圧性粘着剤からなる請求項１記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer comprises a pressure-sensitive pressure-sensitive adhesive.
- 基材の厚さが２０～２００μｍであり、粘着シートの厚さが３０～４００μｍである請求項１記載の粘着シート。 2. The pressure-sensitive adhesive sheet according to claim 1, wherein the thickness of the substrate is 20 to 200 μm and the thickness of the pressure-sensitive adhesive sheet is 30 to 400 μm.
- 以下の引張試験において、引張強度が２０Ｎ／ｍｍ２以上であり、伸びが５００％以上である請求項１記載の粘着シート。
［引張試験］
幅１０ｍｍ、長さ１００ｍｍのサイズの粘着シートを、チャック間隔３０ｍｍに設定した引っ張り試験機に固定し、３００ｍｍ／分の速度で引張り、破断時の引張強度（Ｎ／ｍｍ２）と伸び（％）を測定する。 The pressure-sensitive adhesive sheet according to claim 1, wherein, in the following tensile test, the tensile strength is 20 N / mm 2 or more and the elongation is 500% or more.
[Tensile test]
An adhesive sheet having a width of 10 mm and a length of 100 mm is fixed to a tensile tester set at a chuck interval of 30 mm, pulled at a speed of 300 mm / min, tensile strength at break (N / mm 2 ) and elongation (%) Measure.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020177022529A KR101994568B1 (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
| PCT/JP2015/062059 WO2016170593A1 (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
| JP2017513861A JP6414942B2 (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
| CN201580078909.1A CN108307640B (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2015/062059 WO2016170593A1 (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
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| Publication Number | Publication Date |
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| WO2016170593A1 true WO2016170593A1 (en) | 2016-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2015/062059 WO2016170593A1 (en) | 2015-04-21 | 2015-04-21 | Adhesive sheet |
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| Country | Link |
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| JP (1) | JP6414942B2 (en) |
| KR (1) | KR101994568B1 (en) |
| CN (1) | CN108307640B (en) |
| WO (1) | WO2016170593A1 (en) |
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| KR102530957B1 (en) * | 2020-08-19 | 2023-05-09 | 테사 소시에타스 유로파에아 | Adhesive tape with polyurethane carrier |
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| JPS62176839A (en) * | 1986-01-29 | 1987-08-03 | 東洋化学株式会社 | Extremely thin pressure-sensitive adhesive tape |
| JP2004256595A (en) * | 2003-02-24 | 2004-09-16 | Lintec Corp | Adhesive sheet and method for using the same |
| JP2010189579A (en) * | 2009-02-19 | 2010-09-02 | Kuramoto Sangyo:Kk | Film base material and adhesive sheet |
| JP2011156186A (en) * | 2010-02-02 | 2011-08-18 | Nitto Denko Corp | Pressure-sensitive adhesive tape for medical use |
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| DE4002727A1 (en) * | 1990-01-31 | 1991-08-01 | Bayer Ag | MIXTURES FROM AQUEOUS POLYMER DISPERSIONS |
| DE4431914C2 (en) | 1994-09-08 | 1996-10-17 | Beiersdorf Ag | Strip of an adhesive film for a residue-free, removable adhesive and its use |
| DE10123291A1 (en) | 2001-05-12 | 2002-11-28 | Tesa Ag | Adhesive film strip |
| DE10252089A1 (en) | 2002-11-08 | 2004-05-27 | Tesa Ag | Adhesive and use of the same for a PSA strip made of at least one layer, which can be removed again without leaving any residue and without destruction by stretching it in the bonding plane |
| JP5150436B2 (en) * | 2008-09-26 | 2013-02-20 | 株式会社寺岡製作所 | Heat resistant adhesive tape |
| EP2438128B1 (en) | 2009-06-04 | 2013-04-03 | 3M Innovative Properties Company | Stretch releasable pressure-sensitive adhesives |
| JP2011252095A (en) * | 2010-06-02 | 2011-12-15 | Nitto Denko Corp | Double-coated pressure-sensitive adhesive tape |
| CN102477264B (en) * | 2010-11-26 | 2016-09-07 | 3M创新有限公司 | Double-sided adhesive tape |
| JP5928001B2 (en) * | 2011-03-18 | 2016-06-01 | 株式会社リコー | Developing roller |
| TWI468485B (en) * | 2012-05-21 | 2015-01-11 | Dainippon Ink & Chemicals | Adhesive tape |
| CN105073933B (en) * | 2013-03-29 | 2018-03-30 | Dic株式会社 | Double-faced adhesive tape |
| CN107109148B (en) * | 2014-11-11 | 2021-06-22 | 株式会社寺冈制作所 | Adhesive tape having foamed resin base material and method for producing same |
-
2015
- 2015-04-21 KR KR1020177022529A patent/KR101994568B1/en active IP Right Grant
- 2015-04-21 JP JP2017513861A patent/JP6414942B2/en active Active
- 2015-04-21 CN CN201580078909.1A patent/CN108307640B/en active Active
- 2015-04-21 WO PCT/JP2015/062059 patent/WO2016170593A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62176839A (en) * | 1986-01-29 | 1987-08-03 | 東洋化学株式会社 | Extremely thin pressure-sensitive adhesive tape |
| JP2004256595A (en) * | 2003-02-24 | 2004-09-16 | Lintec Corp | Adhesive sheet and method for using the same |
| JP2010189579A (en) * | 2009-02-19 | 2010-09-02 | Kuramoto Sangyo:Kk | Film base material and adhesive sheet |
| JP2011156186A (en) * | 2010-02-02 | 2011-08-18 | Nitto Denko Corp | Pressure-sensitive adhesive tape for medical use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016170593A1 (en) | 2017-11-24 |
| KR20170141647A (en) | 2017-12-26 |
| JP6414942B2 (en) | 2018-10-31 |
| KR101994568B1 (en) | 2019-06-28 |
| CN108307640A (en) | 2018-07-20 |
| CN108307640B (en) | 2021-10-26 |
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