WO2014156816A1 - Double-sided adhesive tape - Google Patents
Double-sided adhesive tape Download PDFInfo
- Publication number
- WO2014156816A1 WO2014156816A1 PCT/JP2014/057287 JP2014057287W WO2014156816A1 WO 2014156816 A1 WO2014156816 A1 WO 2014156816A1 JP 2014057287 W JP2014057287 W JP 2014057287W WO 2014156816 A1 WO2014156816 A1 WO 2014156816A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- mass
- adhesive tape
- base material
- Prior art date
Links
Images
Classifications
-
- 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
- C09J7/26—Porous or cellular plastics
-
- 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
Definitions
- the present invention relates to a double-sided adhesive tape that can be used for fixing various members including electronic devices.
- the double-sided adhesive tape is used for fixing various electronic equipment members, for example.
- the double-sided adhesive tape is a rigid part such as fixing the protective panel of the image display unit and the casing constituting a small electronic device such as a mobile phone, a camera, a personal computer, an exterior part, a battery, and various member modules. Often used to fix each other.
- a double-sided pressure-sensitive adhesive tape that can be suitably used for fixing components such as small electronic devices
- a thin and good followable tape can be suitably used.
- a flexible foam is used as a base material.
- a double-sided pressure-sensitive adhesive tape is known (for example, see Patent Document 1 or 2).
- the small electronic devices are often used by being carried, and the double-sided pressure-sensitive adhesive tape may be peeled off due to an impact when the electronic devices are dropped, resulting in missing parts. Therefore, the double-sided pressure-sensitive adhesive tape is required to have a level of impact resistance that can withstand the impact of the drop.
- the adhesive tape is required to have a level of disassembly that allows the components to be separated from the electronic device relatively easily and efficiently when a failure of the electronic device occurs.
- the problem to be solved by the present invention is to provide a double-sided pressure-sensitive adhesive tape that has suitable impact resistance and can be easily disassembled when a certain force is applied.
- the present invention is a double-sided pressure-sensitive adhesive tape having pressure-sensitive adhesive layers on both sides of a foam base material, the foam base material having a density of 0.45 g / cm 3 or less and an interlayer strength of 10 N / cm or more.
- the pressure-sensitive adhesive layer is a 25 ⁇ m-thick polyethylene terephthalate base material provided with a 25 ⁇ m-thick pressure-sensitive adhesive layer on an aluminum plate in an environment of a temperature of 23 ° C. and a relative humidity of 65% RH.
- the adhesive force is 12N when peeled by 180 ° at a peeling speed of 300 mm / min measured after being pressed for one hour using a 2 kg roller and allowed to stand in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for 1 hour.
- the above-mentioned problem is solved by a double-sided pressure-sensitive adhesive tape characterized by being a pressure-sensitive adhesive layer of / 20 mm or more.
- the double-sided pressure-sensitive adhesive tape of the present invention has suitable impact resistance due to the above-described configuration, and when a certain force is applied, the foam base material can be easily disassembled by causing an interlaminar crack. For this reason, when an impact such as dropping is applied to an electronic device using the double-sided pressure-sensitive adhesive tape of the present invention, the component is not easily detached, and can be disassembled with a constant force. Can suppress cracking and distortion. In addition, when a specific part is dismantled from a defective product such as the electronic device or a recycled product, it can be disassembled efficiently.
- the double-sided pressure-sensitive adhesive tape of the present invention as described above is used, for example, for fixing parts of small electronic devices, particularly for fixing thin plate-like rigid parts such as protective panels and image display modules for thin electronic devices and image display modules. It can be suitably applied to.
- the double-sided pressure-sensitive adhesive tape of the present invention is a double-sided pressure-sensitive adhesive tape having pressure-sensitive adhesive layers on both sides of a foam substrate, and the foam substrate has a density of 0.45 g / cm 3 or less and an interlayer strength of 10 N / cm or more.
- a pressure-sensitive adhesive tape which is a foam base material and is formed by providing a 25 ⁇ m thick adhesive layer on a 25 ⁇ m thick polyethylene terephthalate base material, in an environment at a temperature of 23 ° C.
- the aluminum plate is crimped by reciprocating once, and then 180 ° peeling at a peeling speed of 300 mm / min measured after standing for 1 hour in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH. It is an adhesive layer having an adhesive strength of 12 N / 20 mm or more.
- the foam substrate for use in the present invention density of 0.45 g / cm 3 or less, preferably 0.1g / cm 3 ⁇ 0.45g / cm 3, more preferably 0.15g / cm 3 ⁇ 0. What is 42 g / cm 3 can be used.
- a foam substrate having a density in the above range it is possible to obtain a double-sided pressure-sensitive adhesive tape having suitable dismantling properties when a certain force is applied.
- foam base material used in the present invention one having an interlayer strength of 10 N / cm or more, preferably 10 N / cm to 50 N / cm, more preferably 10 N / cm to 25 N / cm should be used. Can do.
- a foam base material having an interlayer strength in the above range it is possible to achieve both suitable dismantling properties and suitable impact resistance, and the paste remaining on the surface of the adherend such as parts after dismantling It becomes possible to easily peel off the remaining materials such as.
- the interlayer strength can be measured by the following method.
- One sheet of strong adhesive layer with a thickness of 50 ⁇ m adheresive layer with a level of adhesive that does not peel from the adherend and foam substrate by the following high-speed peel test) on both surfaces of the foam substrate After laminating each one, aging at 40 ° C. for 48 hours creates a double-sided pressure-sensitive adhesive tape for measuring interlayer strength.
- the pressure-sensitive adhesive layer surface on one side of the double-sided pressure-sensitive adhesive tape for measuring the interlayer strength was lined with a polyester film having a thickness of 25 ⁇ m, and cut into a size of 1 cm in the width direction of the foam substrate and 15 cm in the flow direction. After sticking them to a polyester film having a thickness of 50 ⁇ m, a width of 3 cm, and a length of 20 cm under a temperature of 23 ° C. and a relative humidity of 50% RH, the surface was crimped by reciprocating a 2 kg roller, A test piece is obtained by leaving still at 60 degreeC environment for 24 hours, and then leaving still at 23 degreeC for 1 hour.
- the 50 ⁇ m thick polyester film side constituting the test piece is fixed to a mounting jig of a high-speed peel tester, and the test piece is constituted by a 25 ⁇ m thick
- the polyester film is pulled in the direction of 90 degrees at a tensile speed of 15 m / min, the maximum strength when the foam substrate constituting the test piece is torn is measured.
- foam base material those having a 25% compressive strength of 500 kPa or less are preferably used, those having 10 kPa to 300 kPa are more preferable, and those having 10 kPa to 200 kPa are used. More preferably, those having 30 kPa to 180 kPa are more preferably used, and those having 50 kPa to 150 kPa are particularly preferable.
- a foam base material having a compressive strength of 25% within the above range a double-sided pressure-sensitive adhesive tape having both suitable impact resistance and dismantling properties and suitable followability to an adherend is obtained. be able to.
- the 25% compressive strength can be measured according to JISK6767. Specifically, the double-sided pressure-sensitive adhesive tape sample cut into 25 corners is overlaid until the thickness is about 10 mm. The laminate of the double-sided adhesive tape sample is sandwiched between stainless steel plates having a larger area than the double-sided adhesive tape sample, and the laminate of the sample is about 2.5 mm (of the original thickness) at a speed of 10 mm / min at 23 ° C. 25%) Measure the strength when compressed.
- the foam substrate is not particularly limited tensile strength of the flow direction and the width direction, it is preferable to use those having a tensile strength is 500N / cm 2 ⁇ 1300N / cm 2 it is more preferable to use those having a tensile strength is 600N / cm 2 ⁇ 1200N / cm 2.
- the tensile strength of the flow direction and width direction of the above-mentioned foam base material can be measured according to JISK6767. Specifically, the double-sided pressure-sensitive adhesive tape sample cut to a size of a marked line length of 2 cm and a width of 1 cm was used at a tensile speed of 300 mm / min in a 23 ° C. and 50% RH environment using a Tensilon tensile tester. It is the maximum intensity measured under the measurement conditions.
- the foam substrate is not particularly limited in tensile elongation at the time of cutting the foam substrate measured by the tensile test, but the tensile elongation in the flow direction is 100% to 1200%. It is preferable to use those that are 100% to 1000%, more preferably 200% to 600%.
- the average cell diameter in the flow direction and the width direction of the foam substrate is not particularly limited, but is preferably in the range of 10 ⁇ m to 500 ⁇ m, more preferably in the range of 30 ⁇ m to 400 ⁇ m, and in the range of 50 ⁇ m to 300 ⁇ m. More preferably.
- a foam substrate having an average cell diameter in the flow direction and width direction within the above range it is possible to obtain a double-sided pressure-sensitive adhesive tape that is more excellent in adhesion to an adherend and more excellent in impact resistance. it can.
- the ratio of the average bubble diameter in the flow direction and the width direction of the foam substrate is not particularly limited, but may be in the range of 0.2 to 4. Preferably, it is in the range of 0.3 to 3, more preferably in the range of 0.4 to 1.
- the average cell diameter in the thickness direction of the foam substrate is preferably 3 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 80 ⁇ m, and even more preferably 5 ⁇ m to 50 ⁇ m.
- the average cell diameter in the thickness direction is preferably 1/2 or less, and preferably 1/3 or less of the thickness of the foam base material.
- the ratio of the average bubble diameter in the flow direction to the average bubble diameter in the thickness direction (average bubble diameter in the flow direction / average bubble diameter in the thickness direction), and the thickness direction It is preferable to use those in which the ratio of the average bubble diameter in the width direction to the average bubble diameter (average bubble diameter in the width direction / average bubble diameter in the thickness direction) is 1 or more. Some are more preferably used, and more preferably 4 to 25 are used.
- the average cell diameter in the width direction, the average cell diameter in the flow direction, and the average cell diameter in the thickness direction of the foam substrate can be measured in the following manner.
- the foam base material is cut into a size having a width method of 1 cm and a flow direction of 1 cm.
- a digital microscope (trade name “KH-7700”, manufactured by HiROX) is set at a magnification of 200 times, and the cut surface in the width direction or the flow direction of the foam substrate is observed. In that case, the full length of the thickness direction of the cut surface of the said foam base material is observed. In the observation, all the bubble diameters of the bubbles existing in the range of 2 mm in the flow direction or the width direction of the cut surface are measured. Next, the range of 2 mm is changed, and all the bubble diameters of bubbles existing in arbitrary 10 ranges are measured.
- the value obtained by calculating the average value of the bubble diameters measured above was defined as the average bubble diameter.
- the foam base material it is preferable to use a foam base material because it can effectively prevent water immersion or dust from the cut surface of the foam base material.
- the average bubble diameter in the flow direction or width direction or in both directions is larger than the average bubble diameter in the thickness direction. It is preferable for obtaining a double-sided pressure-sensitive adhesive tape having excellent followability and cushioning properties.
- one having a thickness of 250 ⁇ m or less is preferably used, one having a thickness of 50 ⁇ m to 250 ⁇ m is more preferable, and one having a thickness of 80 ⁇ m to 200 ⁇ m is further used.
- the use of one having a thickness of 100 ⁇ m to 150 ⁇ m is particularly preferable in order to obtain a double-sided pressure-sensitive adhesive tape having even better impact resistance and dismantling properties even if it is thin.
- the density, interlayer strength, compressive strength, tensile strength, and the like of the foam base material can be appropriately adjusted depending on the material and foam structure of the foam base material to be used.
- foam base material examples include polyolefin-based foams, polyurethane-based foams, and acrylic-based foams obtained using polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and the like. Other rubber-based foams can be used.
- foam base material among those described above, polyolefin foam is used because it is easy to produce a foam base material having a closed cell structure that can suitably follow the surface irregularities of the adherend and has excellent impact resistance. It is preferable to do.
- the polyolefin-based foam base material it is preferable to use a foam base material obtained by using a polyethylene-based resin because it has a relatively uniform thickness and more suitable flexibility.
- the content of the polyethylene resin contained in the polyolefin resin is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 100% by mass. % Is particularly preferred.
- polyethylene resin examples include linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ethylene- ⁇ containing 50% by mass or more of ethylene.
- An olefin copolymer, an ethylene-vinyl acetate copolymer containing 50% by mass or more of ethylene can be used alone or in combination of two or more.
- Examples of the ⁇ -olefin constituting the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Is mentioned.
- the polypropylene resin is not particularly limited, and examples thereof include polypropylene and a propylene- ⁇ -olefin copolymer containing 50% by mass or more of propylene, and these may be used alone or in combination of two or more. You may use together.
- Examples of the ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Can be mentioned.
- the polyethylene resin it is preferable to use a polyethylene resin having a narrow molecular weight distribution obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst.
- the polyethylene resin obtained by the above method can adjust the copolymerization ratio of the copolymerization component to be almost equal even if it is a polyethylene resin having any molecular weight.
- a polyolefin foam can be obtained.
- the substantially uniformly crosslinked polyolefin-based foam can be easily stretched, and the thickness thereof can be easily uniformed as a whole.
- polyethylene-based resin a polyolefin-based resin obtained by another manufacturing method other than that obtained using a metallocene compound containing a tetravalent transition metal may be used.
- the polyolefin-based foam substrate may have a crosslinked structure.
- a polyolefin-based foam by foaming a polyolefin-based resin sheet with a pyrolytic foaming agent or the like, it is preferable to design to form the crosslinked structure.
- the degree of crosslinking is preferably in the range of 5% by mass to 60% by mass, and more preferably in the range of 10% by mass to 55% by mass to achieve better adhesion to the pressure-sensitive adhesive layer and impact resistance. It is more preferable in improving.
- the degree of crosslinking can be measured by the following method. A set of five 40 mm ⁇ 50 mm square foam base materials is used as a sample, and the total mass (G1) is measured. Next, after immersing the sample in xylene at 120 ° C. for 24 hours, the xylene-insoluble matter was separated by filtration through a 300 mesh wire net, and the residue mass (G2) after drying at 110 ° C. for 1 hour was measured. To do. The xylene-insoluble content determined according to the following formula is defined as the degree of crosslinking.
- the method for producing the polyolefin foam is not particularly limited.
- a polyolefin resin containing 40% by weight or more of a polyethylene resin obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst and A polyolefin-based resin composition containing a pyrolytic foaming agent, a foaming aid, and a colorant for coloring the foam in black or white is supplied to an extruder and melt-kneaded.
- stretching a foam sheet should just be performed as needed, and may be performed in multiple times.
- the pyrolytic foaming agent is not particularly limited as long as it is conventionally used in the production of foams.
- azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl Semicarbazide and the like can be mentioned, and among them, azodicarbonamide is preferable.
- a thermal decomposition type foaming agent may be individual, or 2 or more types may be used together.
- the amount of the pyrolytic foaming agent added may be appropriately determined according to the foaming ratio of the polyolefin foam, but is preferably 1 part by weight to 40 parts by weight with respect to 100 parts by weight of the polyolefin resin.
- the amount of 1 to 30 parts by mass is more preferable because the expansion ratio, tensile strength, compression recovery rate, and the like can be easily adjusted to a desired range.
- a method of crosslinking the polyolefin foam substrate for example, a method of irradiating the polyolefin foam substrate with ionizing radiation, an organic peroxide was previously blended in the polyolefin resin composition, and obtained.
- disassembling an organic peroxide etc. is mentioned, These methods may be used together.
- ionizing radiation examples include electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- the dose of ionizing radiation can be appropriately adjusted so that the cross-linking degree of the polyolefin-based foam substrate is within the above preferred range, but is preferably in the range of 5 kGy to 200 kGy.
- organic peroxide examples include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis ( t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ ′ -Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexyne-3, benzoyl peroxide, cumyl peroxyneodecanate, t-butyl peroxybenzoate, 2,5
- the organic peroxide is preferably in the range of 0.01 parts by mass to 5 parts by mass, and in the range of 0.1 parts by mass to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is more preferable for suppressing the residue of the decomposition residue of the organic peroxide.
- the method of foaming the polyolefin resin sheet is not particularly limited, and examples thereof include a method of heating with hot air, a method of heating with infrared rays, a method using a salt bath, a method using an oil bath, and the like. May be. Among them, the method of heating with hot air or the method of heating with infrared rays is preferable because the difference in appearance between the front and back surfaces of the polyolefin-based foam substrate is reduced.
- the foam base material may be stretched.
- the stretching may be performed after foaming the polyolefin resin sheet to obtain a foam substrate, or may be performed when foaming the polyolefin resin sheet.
- the foam base material After foaming a polyolefin resin sheet to obtain a foam base material, when the foam base material is stretched, the foam base material is continuously maintained while maintaining the molten state at the time of foaming without cooling the foam base material. Even after stretching, the foam base material may be stretched after cooling the foam base material and heating the foam sheet again to a molten or softened state.
- the molten state of the foam base material means a state in which the foam base material is heated to a melting point or higher of the polyolefin resin constituting the foam base material.
- the softening of the foam base material refers to a state where the foam base material is heated to a temperature not lower than the melting point and lower than the melting point of the polyolefin resin constituting the foam base material.
- the stretching direction of the foam substrate is preferably in the flow direction or the width direction of the long polyolefin resin sheet, or in the flow direction and the width direction.
- the foam base material may be stretched simultaneously in the flow direction and the width direction, or may be stretched separately one by one. .
- a method of stretching the foam base material in the flow direction for example, a long polyolefin resin sheet after foaming is used rather than a speed (supply speed) at which the long polyolefin resin sheet is supplied to the foaming process.
- a method of stretching the foam base material in the flow direction by increasing the winding speed (winding speed) while cooling, foaming rather than the speed (supply speed) of supplying the obtained foam base material to the stretching process Examples include a method of stretching the foam base material in the flow direction by increasing the speed of winding the body base material (winding speed).
- the polyolefin resin sheet easily expands in the flow direction due to its own foaming, when the foam base material obtained using the polyolefin resin sheet is stretched in the flow direction, the polyolefin resin sheet Considering the amount of expansion in the flow direction due to foaming, it is preferable to adjust the supply speed and winding speed of the foam substrate so that the polyolefin resin sheet is stretched in the flow direction more than the expansion amount. .
- both ends in the width direction of the foam base material are gripped by a pair of gripping members, and the pair of gripping members are gradually moved in directions away from each other.
- a method of stretching the foam base material in the width direction is preferred. Since the polyolefin resin sheet expands in the width direction by its own foaming, when the foam base material is stretched in the width direction, the expansion in the width direction due to the foaming of the polyolefin resin sheet is taken into account. Above, it is preferable to adjust so that a foam base material may be extended
- the draw ratio in the flow direction of the foam substrate is preferably 1.1 to 5 times, more preferably 1.3 to 3.5 times.
- the draw ratio in the width direction is preferably 1.2 to 4.5 times, and more preferably 1.5 to 3.5 times.
- a colored foam base material may be used in order to obtain an adhesive tape having design properties, light shielding properties, concealing properties, light reflectivity, light resistance, and the like.
- a conventionally known coloring agent can be used individually or in combination of 2 or more types.
- the light-shielding property, the concealing property and the light resistance are imparted to the adhesive tape, it is preferable to use a material colored black as the foam base material.
- the black colorant examples include carbon black, graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, cyanine black, activated carbon, ferrite, magnetite, chromium oxide, iron oxide, molybdenum disulfide, and chromium complex.
- Complex oxide black dyes, anthraquinone organic black dyes, and the like can be used.
- carbon black it is preferable to use carbon black from the viewpoint of cost, availability, insulation, and heat resistance at a level that can withstand the temperature of the process of extruding the polyolefin resin composition and the heating and foaming process. .
- the design and light reflectivity are imparted to the adhesive tape, it is preferable to use a white colored one as the foam base material.
- the white colorant examples include titanium oxide, zinc oxide, aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, calcium oxide, tin oxide, barium oxide, cesium oxide, yttrium oxide, magnesium carbonate, calcium carbonate, barium carbonate, Zinc carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, aluminum silicate, calcium silicate, barium sulfate, calcium sulfate, barium stearate, zinc white, talc, silica, alumina, clay, kaolin, Inorganic white colorants such as titanium phosphate, mica, gypsum, white carbon, diatomaceous earth, bentonite, lithopone, zeolite, sericite, silicone resin particles, acrylic resin particles, urethane resin particles, melamine resin particles And the like can be used organic white colorants such as.
- titanium oxide, aluminum oxide, or zinc oxide should be used from the viewpoint of cost, availability, color tone, heat resistance that can withstand the temperature of the process of extruding the polyolefin resin composition and the heating and foaming process. Is preferred.
- the foam base material may be a plasticizer, an antioxidant, a foaming aid such as zinc oxide, a cell core modifier, a heat stabilizer, a flame retardant such as aluminum hydroxide or magnesium hydroxide, and an antistatic agent. It may contain known agents such as agents, fillers such as glass or plastic hollow balloons / beads, metal powders, metal compounds, conductive fillers, and heat conductive fillers.
- the colorant, the thermally decomposable foaming agent, the foaming auxiliary agent, etc. in order to prevent poor appearance such as uneven color shading, and poor foaming such as excessive foaming and non-foaming, a polyolefin resin, or It is preferable that the masterbatch is made of another thermoplastic resin that is easily compatible with the polyolefin resin.
- foam base material surface treatment such as corona treatment, flame treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, and easy adhesion treatment is performed in order to improve the adhesion with the pressure-sensitive adhesive layer and other layers.
- surface treatment such as corona treatment, flame treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, and easy adhesion treatment is performed in order to improve the adhesion with the pressure-sensitive adhesive layer and other layers.
- the applied one can be used.
- the surface of the surface-treated foam base material preferably has a wetting index by a wetting reagent of 36 mN / m or more, preferably 40 mN / m or more, and 48 mN / m or more. It is further preferable for maintaining good adhesion with a layer or the like.
- the foam base material with improved adhesion may be bonded to the adhesive layer in a continuous process. Further, the foam base material with improved adhesion may be temporarily wound up and stored, and then bonded to the adhesive layer at a later date.
- the foam base material having improved adhesion when winding up the foam base material having improved adhesion, it is preferable to wind it through a film made of paper, polyethylene, polypropylene, polyester, or the like in order to prevent blocking of the foam base material.
- the film is preferably a polypropylene film or a polyester film having a thickness of 25 ⁇ m or less.
- the adhesive layer which the double-sided adhesive tape of this invention has is provided in the front and back (both surfaces) of a foam base material. At least one of the pressure-sensitive adhesive layers provided on each surface, preferably both pressure-sensitive adhesive layers are formed by forming a pressure-sensitive adhesive tape formed by providing a 25 ⁇ m-thick pressure-sensitive adhesive layer on a 25 ⁇ m-thick polyethylene terephthalate substrate. Measured after pressure-bonding to an aluminum plate by reciprocating once using an aluminum plate in an environment of °C and relative humidity of 65% RH, and standing for 1 hour in an environment of temperature of 23 °C and relative humidity of 50% RH.
- a pressure-sensitive adhesive layer having a 180 ° peeling adhesive strength of 12 N / 20 mm or more at a peeling speed of 300 mm / min.
- the pressure-sensitive adhesive layer it is preferable to use a layer having a 180 ° peeling adhesive strength of 10 N / 20 mm or more, and a layer having a 180 ° peeling adhesive strength of 12 N / 20 mm or more can be used at the time of disassembly. It is preferable to obtain a double-sided pressure-sensitive adhesive tape that can realize interlaminar cracking of the foam base material by applying a certain force and has excellent impact resistance.
- the upper limit of the 180 ° peeling adhesion is not particularly limited, but is preferably 25 N / 20 mm or less, and more preferably 20 N / 20 mm or less.
- the pressure-sensitive adhesive composition capable of forming the pressure-sensitive adhesive layer for example, a (meth) acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like is used. Can do.
- a (meth) acrylic pressure-sensitive adhesive for example, a (meth) acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like is used.
- the pressure-sensitive adhesive composition it is desirable to use an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer and containing additives such as a tackifier resin and a crosslinking agent as necessary. It is preferable for forming a pressure-sensitive adhesive layer having a 180 ° peeling adhesive strength.
- Examples of the (meth) acrylate that can be used for the production of the acrylic polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) ) Acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.
- Examples thereof include (meth) acrylates having 12 to 12 alkyl groups, and one or more of these can be used. Among them, it is preferable to use (meth) acrylate having an alkyl group having 4 to 12 carbon atoms, and to use (meth) acrylate having a linear or branched alkyl group having 4 to 8 carbon atoms. More preferably, the use of one or more selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate is preferable in forming a pressure-sensitive adhesive layer having a desired 180 ° peel-off adhesive strength and the like.
- the (meth) acrylate having an alkyl group having 1 to 12 carbon atoms is preferably used in an amount of 60% by mass or more, based on the total amount of monomer components used in the production of the acrylic polymer, and 80% by mass. % To 98.5% by mass is more preferable, and 90% to 98.5% by mass is more preferable.
- a highly polar vinyl monomer can be used as a monomer component.
- the highly polar vinyl monomer include a vinyl monomer having a hydroxyl group, a vinyl monomer having a carboxyl group, a vinyl monomer having an amide group, etc., and one or more of these are used. can do.
- vinyl monomer having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like.
- (Meth) acrylates having the following can be used.
- acrylic acid for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, (meth) acrylic acid dimer, crotonic acid, ethylene oxide-modified oxalic acid acrylate, etc.
- acrylic acid is preferably used.
- vinyl monomer having an amide group for example, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide and the like can be used.
- vinyl monomers having a sulfonic acid group such as vinyl acetate, ethylene oxide-modified succinic acid acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and the like can be used.
- the high-polarity vinyl monomer is preferably used in a range of 1.5% by mass to 20% by mass with respect to the total amount of monomer components used in the production of the acrylic polymer. It is more preferable to use in the range of 10% by mass to 10% by mass, and it is preferable to use in the range of 2% by mass to 8% by mass in order to form a pressure-sensitive adhesive layer having a desired 180 ° peeling adhesive strength. preferable.
- the acrylic polymer which has a functional group which reacts with the isocyanate group.
- a vinyl monomer having a hydroxyl group is preferably used as the monomer component that can be used in this case.
- the vinyl monomer having a hydroxyl group is preferably used in the range of 0.01% by mass to 1.0% by mass with respect to the total of the monomer components used in the production of the acrylic polymer. It is more preferable to use in the range of 0.03 mass% to 0.3 mass%.
- the acrylic polymer can be produced by polymerizing the monomer component.
- the polymerization method include known polymerization methods such as a solution polymerization method, a cage polymerization method, a suspension polymerization method, and an emulsion polymerization method, and a solution for obtaining a pressure-sensitive adhesive composition having good water resistance. It is preferable to employ a polymerization method or a bulk polymerization method.
- a method using a peroxide thermal polymerization initiator such as benzoyl peroxide or lauroyl peroxide, an azo thermal polymerization initiator such as azobisisobutylnitrile, an acetophenone photopolymerization initiator, a benzoin ether photopolymer Polymerization initiator, benzyl ketal photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, benzoin photopolymerization initiator, a method using a benzophenone photopolymerization initiator, a method of irradiating an electron beam, Can be advanced.
- a peroxide thermal polymerization initiator such as benzoyl peroxide or lauroyl peroxide
- an azo thermal polymerization initiator such as azobisisobutylnitrile
- an acetophenone photopolymerization initiator a benzoin ether photopolymer Polymerization initiator
- acrylic polymer those having a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) in the range of 400,000 to 3 million are preferably used. It is more preferable to use one having a range of 2.5 million.
- GPC gel permeation chromatography
- the molecular weight measurement by the GPC method is a standard polystyrene conversion value measured using a GPC apparatus (HLC-8329GPC) manufactured by Tosoh Corporation, and the measurement conditions are as follows.
- a pressure-sensitive adhesive composition used in the present invention it is preferable to use a pressure-sensitive adhesive composition containing a tackifying resin for the purpose of further improving the adhesion to the adherend and the surface adhesion strength.
- tackifier resins include rosin-based tackifier resins, polymerized rosin-based tackifier resins, polymerized rosin ester-based tackifier resins, rosin phenol-based tackifier resins, stabilized rosin ester-based tackifier resins, and disproportionated rosin ester-based tackifiers.
- An imparting resin a hydrogenated rosin ester tackifier resin, a terpene tackifier resin, a terpene phenol tackifier resin, a petroleum resin tackifier resin, a (meth) acrylate resin tackifier resin, or the like can be used.
- tackifying resin disproportionated rosin ester tackifying resin, polymerized rosin ester tackifying resin, rosin phenol tackifying resin, hydrogenated rosin ester tackifying resin, (meth) acrylate resin It is preferable to use a tackifier resin and a terpene phenol tackifier resin alone or in combination of two or more.
- an emulsion-type pressure-sensitive adhesive composition is used as the pressure-sensitive adhesive composition, it is preferable to use an emulsion-type pressure-sensitive adhesive resin as the tackifier resin.
- the tackifying resin those having a softening point of 30 ° C. to 180 ° C. are preferably used, and those having a softening point of 70 ° C. to 140 ° C. are preferably used for peeling off at 180 °. It is preferable when forming a pressure-sensitive adhesive layer having the above.
- the (meth) acrylate tackifying resin preferably has a glass transition temperature of 30 ° C. to 200 ° C., preferably 50 ° C. to 160 ° C. It is more preferable to use those.
- the tackifying resin is preferably used in the range of 5 to 65 parts by mass, and preferably in the range of 8 to 55 parts by mass with respect to 100 parts by mass of the acrylic polymer. It is preferable for forming a pressure-sensitive adhesive layer having a 180 ° peeling adhesive strength.
- the pressure-sensitive adhesive composition in addition to the acrylic polymer and tackifying resin, it is preferable to use a material containing a crosslinking agent as necessary in order to form a pressure-sensitive adhesive layer having a high cohesive force. .
- crosslinking agent for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal chelate crosslinking agent, an aziridine crosslinking agent, or the like can be used.
- the cross-linking agent it is preferable to use an isocyanate cross-linking agent and an epoxy cross-linking agent rich in reactivity with an acrylic polymer alone or in combination, and the use of an isocyanate cross-linking agent is a pressure-sensitive adhesive. This is preferable because the adhesion between the layer and the foam substrate can be further improved.
- the isocyanate-based crosslinking agent for example, tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane modified tolylene diisocyanate and the like can be used.
- said isocyanate type crosslinking agent it is preferable to use what has three or more isocyanate groups, Specifically, the trimethylol propane adduct of tolylene diisocyanate, a triphenylmethane triisocyanate, etc. are mentioned. .
- plasticizers in addition to the above-described components, plasticizers, softeners, antioxidants, flame retardants, glass and plastic fibers, balloons, beads, metal powders, metal oxides, metals as necessary
- additives such as fillers such as nitrides, colorants such as pigments and dyes, leveling agents, thickeners, water repellents, and antifoaming agents can be used.
- the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition it is desirable to use a layer having a temperature at which the peak value of loss tangent (tan ⁇ ) at a frequency of 1 Hz is in the range of ⁇ 40 ° C. to 15 ° C. It is preferable for providing a good adhesion with an adherend at room temperature at a normal temperature.
- the pressure-sensitive adhesive layer the one having the temperature of ⁇ 35 ° C. to 10 ° C. has a desired 180 ° peel-off adhesive force and good adhesion to the adherend at room temperature. It is preferable to further improve the impact resistance in a low temperature environment, and it is more preferable to use a material having a temperature of ⁇ 30 ° C. to 6 ° C.
- a pressure-sensitive adhesive layer formed to a thickness of about 2 mm was used using a viscoelasticity testing machine (trade name: ARES G2 manufactured by T.A. Instruments Japan).
- a test piece is sandwiched between parallel disks having a diameter of 8 mm, which is a measuring part, and a storage elastic modulus (G ′) and a loss elastic modulus (G ′′) from ⁇ 50 ° C. to 150 ° C. are measured at a frequency of 1 Hz.
- the thickness of the pressure-sensitive adhesive layer is preferably in the range of 5 ⁇ m to 100 ⁇ m in order to provide a desired 180 ° peel-off adhesive force and, as a result, further improve the adhesion to the adherend.
- a range of 80 ⁇ m is more preferable, and a range of 15 ⁇ m to 80 ⁇ m is more preferable.
- the double-sided pressure-sensitive adhesive tape of the present invention is, for example, a direct copy method in which an adhesive is applied and dried directly on a foam base material or on the surface of another layer laminated on the foam base material, and sticks to a release sheet. After the agent is applied and dried, it can be produced by a transfer method in which it is bonded to the surface of the foam substrate or other layer.
- the double-sided pressure-sensitive adhesive tape is preferably used in an environment of 20 ° C. to 50 ° C., more preferably 23 ° C. to 45 ° C. Aging for 2 to 7 days can provide the desired 180 ° peel-off adhesive force, and can further improve the adhesion between the foam substrate and the pressure-sensitive adhesive layer.
- the release sheet is not particularly limited, but is adhered to at least one surface of a base material such as a synthetic resin film such as polyethylene, polypropylene, or polyester film, paper, nonwoven fabric, cloth, foam sheet or metal foil, and a laminate thereof.
- a base material such as a synthetic resin film such as polyethylene, polypropylene, or polyester film, paper, nonwoven fabric, cloth, foam sheet or metal foil, and a laminate thereof.
- a material that has been subjected to a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment for improving the releasability from the agent can be used.
- release sheet high-quality paper laminated on both sides with polyethylene having a thickness of 10 to 40 ⁇ m, or one having both sides of a polyester film base material subjected to silicone-based release treatment may be used. preferable.
- An embodiment of the pressure-sensitive adhesive tape of the present invention has a basic structure in which a foam base material is a core, and a pressure-sensitive adhesive layer is provided on at least one surface, preferably both surfaces of the foam base material.
- the foam substrate and the pressure-sensitive adhesive layer may be directly laminated or may be laminated via another layer.
- the adhesive tape may have other layers as required in addition to the foam base material and the adhesive layer.
- laminate layers such as a polyester film.
- a metal You may have the layer which consists of a nonwoven fabric plated with foil or a metal mesh electroconductive metal.
- a film such as a polyester film such as polyethylene terephthalate, a polyethylene film, or a polypropylene film can be used.
- the thickness of the laminate layer is not particularly defined, but is preferably in the range of 1 ⁇ m to 25 ⁇ m, more preferably in the range of 2 ⁇ m to 12 ⁇ m, in order to ensure good followability to the foam substrate. .
- a conventionally known pressure-sensitive adhesive or an adhesive for dry lamination can be used.
- the light shielding layer examples include a layer printed with an ink containing a colorant such as a pigment, and a layer printed with black ink can be preferably used.
- the reflective layer examples include a layer printed with an ink containing a colorant such as a pigment, and a layer printed with white ink can be preferably used.
- the thickness of the light-shielding layer and the reflective layer is preferably 2 ⁇ m to 20 ⁇ m, and preferably 4 ⁇ m to 6 ⁇ m because curling of the adhesive tape due to the curing shrinkage of the ink can be suppressed.
- the total thickness of the double-sided pressure-sensitive adhesive tape of the present invention obtained by the above method may be appropriately adjusted depending on the mode of use, but is preferably 300 ⁇ m or less, more preferably 80 ⁇ m to 300 ⁇ m, and more preferably 100 ⁇ m to 300 ⁇ m. It is more preferable because it is thin and can have both excellent impact resistance and dismantling properties and contribute to the thinning of a small electronic terminal.
- the pressure-sensitive adhesive tape of the present invention has suitable impact resistance and dismantling properties according to the above-described configuration, so that it is a component of a small electronic device, for example, a protection panel or an image display module for an information display unit of a small electronic device, Fixing speakers, receivers, piezoelectric elements, printed circuit boards, flexible printed circuit boards (FPCs), digital camera modules, sensors, other modules, cushioning rubber members such as polyurethane and polyolefin, decorative parts and various members It can be suitably applied to.
- the present invention can be suitably applied to fixing a thin plate-like rigid part such as a protection panel, an image display module, or a thin battery for an information display unit of a small electronic device.
- the pressure-sensitive adhesive composition (a) 100 parts by mass of the pressure-sensitive adhesive composition (a) and 1.3 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, non-volatile content: 45% by mass) are mixed. The mixture was stirred for 15 minutes to obtain a pressure-sensitive adhesive composition (A).
- the adhesive composition (A) had a 180 ° peel adhesion of 12 N / 20 mm. The 180 ° peel adhesion is a value measured by the method described later.
- the pressure-sensitive adhesive composition (A) was applied to a polyethylene terephthalate substrate having a thickness of 25 ⁇ m so that the thickness of the pressure-sensitive adhesive layer after drying was 25 ⁇ m, dried at 80 ° C. for 3 minutes, and then heated to 40 ° C. An adhesive tape was obtained by aging in an environment for 48 hours.
- the adhesive tape is affixed to an aluminum plate in an environment of a temperature of 23 ° C. and a relative humidity of 65% RH, and the upper surface of the adhesive tape (the surface on the polyethylene terephthalate substrate side) is reciprocated once using a 2 kg roller. Crimped them with.
- the material pressure-bonded by the above method was left to stand in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for 1 hour, and then the strength when peeled by 180 ° at a peeling speed of 300 mm / min was measured.
- the 180 ° peel adhesive strength of the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive compositions (B) to (D) described later was also measured by the same method as described above.
- the pressure-sensitive adhesive composition (c) 100 parts by mass of the pressure-sensitive adhesive composition (c) and 1.3 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, non-volatile content: 45% by mass) were mixed for 15 minutes.
- the pressure-sensitive adhesive composition (C) was obtained by stirring.
- the adhesive composition (C) had a 180 ° peel-off adhesive strength of 12.8 N / 20 mm.
- the pressure-sensitive adhesive composition (d) 100 parts by mass of the pressure-sensitive adhesive composition (d) and 1.3 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, nonvolatile content: 45% by mass) were mixed for 15 minutes.
- the pressure-sensitive adhesive composition (D) was obtained by stirring.
- the adhesive composition (D) had a 180 ° peel adhesion of 13.2 N / 20 mm.
- the pressure-sensitive adhesive composition (e) 100 parts by mass of the pressure-sensitive adhesive composition (e) and 1.3 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, non-volatile content: 45% by mass) were mixed for 15 minutes.
- the pressure-sensitive adhesive composition (E) was obtained by stirring.
- the adhesive composition (E) had a 180 ° peel-off adhesive strength of 12.3 N / 20 mm.
- the pressure-sensitive adhesive composition (f) 100 parts by mass of the pressure-sensitive adhesive composition (f) and 0.9 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based cross-linking agent, nonvolatile content: 45% by mass) were mixed for 15 minutes.
- the pressure-sensitive adhesive composition (F) was obtained by stirring.
- the adhesive composition (F) had a 180 ° peel adhesion of 8.5 N / 20 mm.
- the pressure-sensitive adhesive composition (g) 100 parts by mass of the pressure-sensitive adhesive composition (g) and 1.1 parts by mass of “Coronate L-45” (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, non-volatile content: 45% by mass) were mixed for 15 minutes.
- the pressure-sensitive adhesive composition (G) was obtained by stirring.
- the adhesive composition (G) had a 180 ° peel adhesion of 8.9 N / 20 mm.
- Example 1 By coating the pressure-sensitive adhesive composition (A) on the peel-treated surface of a 75 ⁇ m-thick polyethylene terephthalate film (PET film) to a thickness of 25 ⁇ m after drying, and drying at 80 ° C. for 3 minutes. An adhesive layer was formed. The gel fraction of the pressure-sensitive adhesive layer was 42.5% by mass.
- PET film polyethylene terephthalate film
- black polyolefin-based foam (1) (thickness 100 ⁇ m, density 0.40 g / cm 3 , interlayer strength 12.6 N / cm, 25% compression strength: 103 kPa, tensile strength in the flow direction: 1084 N / cm 2
- the pressure-sensitive adhesive is applied to both sides of a base material made of Sekisui Chemical Co., Ltd. foam surface having a wetting index of 54 mN / m by tensile strength in the width direction: 790 N / cm 2 .
- a double-sided adhesive tape with a thickness of 150 ⁇ m was obtained. It was.
- Example 2 A double-sided pressure-sensitive adhesive tape having a thickness of 130 ⁇ m was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 25 ⁇ m to 15 ⁇ m.
- Example 3 A double-sided pressure-sensitive adhesive tape having a thickness of 200 ⁇ m was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 25 ⁇ m to 50 ⁇ m.
- Example 4 instead of the black polyolefin foam (1), the black polyolefin foam (2) (thickness: 80 ⁇ m, density 0.40 g / cm 3 , interlayer strength 10.2 N / cm, 25% compression strength: 92 kPa, flow The tensile strength in the direction: 1062 N / cm 2 , the tensile strength in the width direction: 962 N / cm 2 , and the surface of the foam made by Sekisui Chemical Co., Ltd.
- a double-sided pressure-sensitive adhesive tape having a thickness of 110 ⁇ m was obtained in the same manner as in Example 1 except that the thickness after drying of the pressure-sensitive adhesive layer was changed from 25 ⁇ m to 15 ⁇ m.
- Example 5 Black polyolefin foam (3) instead of black polyolefin foam (1) (thickness: 100 ⁇ m, density 0.45 g / cm 3 , interlayer strength 16.2 N / cm, 25% compressive strength: 190 kPa, flow direction
- the surface of the foam made by Sekisui Chemical Co., Ltd. having a tensile strength of 964 N / cm 2 and a width direction tensile strength of 861 N / cm 2 is obtained by corona treatment with a wetting index of 54 mN / m)
- a double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that it was not.
- Example 6 A double-sided pressure-sensitive adhesive tape having a thickness of 200 ⁇ m was obtained in the same manner as in Example 5 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 ⁇ m to 50 ⁇ m.
- Example 7 Black polyolefin foam (4) instead of black polyolefin foam (1) (thickness: 140 ⁇ m, density 0.40 g / cm 3 , interlayer strength 19.1 N / cm, 25% compressive strength: 130 kPa, flow direction
- the surface of the foam made by Sekisui Chemical Co., Ltd. with a tensile strength of 994 N / cm 2 and a width direction tensile strength of 713 N / cm 2 was used to obtain a wet index of 54 mN / m by corona treatment.
- a double-sided pressure-sensitive adhesive tape having a thickness of 200 ⁇ m was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 ⁇ m to 30 ⁇ m.
- Example 8 A double-sided pressure-sensitive adhesive tape having a thickness of 250 ⁇ m was obtained in the same manner as in Example 7, except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 30 ⁇ m to 55 ⁇ m.
- Example 9 A double-sided pressure-sensitive adhesive tape having a thickness of 300 ⁇ m was obtained in the same manner as in Example 7, except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 30 ⁇ m to 80 ⁇ m.
- Example 10 A double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (B) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 40% by mass).
- Example 11 A double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (C) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 43% by mass).
- Example 12 A double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (D) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 25% by mass).
- Example 13 A double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (E) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 39% by mass).
- Comparative Example 3 A double-sided pressure-sensitive adhesive tape having a thickness of 200 ⁇ m was obtained in the same manner as in Comparative Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 ⁇ m to 50 ⁇ m.
- Example 4 A double-sided pressure-sensitive adhesive tape having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (F) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 38% by mass).
- Example 5 A double-sided pressure-sensitive adhesive tape having a thickness of 200 ⁇ m was obtained in the same manner as in Example 7 except that the pressure-sensitive adhesive composition (G) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 48% by mass).
- Foam substrate and adhesive tape thickness The thickness of the foam base material was measured using a dial series gauge G type manufactured by Ozaki Seisakusho. The thickness of the pressure-sensitive adhesive tape was measured by using a dial thickness gauge G type after peeling the release film.
- the density of the foam substrate was measured according to JISK6767. Specifically, a foam base material cut into a 4 cm ⁇ 5 cm rectangle was prepared for 15 cm 3 minutes, and the mass was measured to determine the density.
- the adhesive surface on one side of the double-sided adhesive tape was lined with a polyester film having a thickness of 25 ⁇ m, and then cut into a size of 1 cm in the width direction of the foam base material and 15 cm in the flow direction. Affixed to a polyester film having a relative humidity of 50% RH, a thickness of 50 ⁇ m, a width of 3 cm, and a length of 20 cm. The test piece was obtained by leaving still at time and then leaving still at 23 degreeC for 1 hour.
- the polyester film side of 50 ⁇ m thickness constituting the test piece is fixed to a mounting jig of a high-speed peel tester, and the 25 ⁇ m thick polyester constituting the test piece is fixed.
- the film By pulling the film in the direction of 90 degrees at a tensile speed of 15 m / min, the maximum strength when the foam base material constituting the test piece was torn was measured.
- the polycarbonate plate on which the PET film is wound and fixed is adhered and fixed to the surface of an aluminum plate having a length of 20 cm and a width of 20 cm so that the double-sided adhesive tape comes into contact with the polycarbonate plate, and pressure-bonded using a 2 kg weight. .
- the test piece was left standing at 23 ° C. and 50% RH for 72 hours.
- A The entire surface of the double-sided adhesive tape was broken and peeled between the layers of the foam base material.
- ⁇ 90% or more of the double-sided adhesive tape was broken and peeled between the layers of the foam substrate.
- a U-shaped measuring table (made of aluminum with a thickness of 5 mm) having a length of 150 mm, a width of 100 mm and a height of 45 mm is installed on the base of the DuPont impact tester (manufactured by Tester Sangyo Co., Ltd.). The test piece was placed on top with the acrylic plate facing down (FIG. 3). A stainless steel striker with a diameter of 25 mm and a mass of 300 g from the ABS plate side is changed in height by 10 cm and dropped 5 times at 10-second intervals from the height to the center of the ABS plate, and the tape is peeled off from the test piece. The height at which breakage was observed was measured.
- the double-sided pressure-sensitive adhesive tape of the present invention had excellent drop impact resistance and easy disassembly (interlaminar cracking) with the adherend.
- the double-sided pressure-sensitive adhesive tapes of Comparative Examples 1 to 6 did not have sufficient resistance to drop impact, or were inferior in easy disassembly (interlaminar cracking).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明に使用する発泡体基材としては、密度が0.45g/cm3以下、好ましくは0.1g/cm3~0.45g/cm3、より好ましくは0.15g/cm3~0.42g/cm3であるものを使用することができる。前記範囲の密度を有する発泡体基材を使用することによって、一定の力が加わった際の好適な解体性を備えた両面粘着テープを得ることができる。 [Foam substrate]
The foam substrate for use in the present invention, density of 0.45 g / cm 3 or less, preferably 0.1g / cm 3 ~ 0.45g / cm 3, more preferably 0.15g / cm 3 ~ 0. What is 42 g / cm 3 can be used. By using a foam substrate having a density in the above range, it is possible to obtain a double-sided pressure-sensitive adhesive tape having suitable dismantling properties when a certain force is applied.
本発明の両面粘着テープが有する粘着剤層は、発泡体基材の表裏面(両面)に設けられる。各面に設けられる粘着剤層のうち、少なくとも一方、好ましくは両方の粘着剤層は、厚さ25μmのポリエチレンテレフタレート基材に厚さ25μmの粘着剤層を設けて形成した粘着テープを、温度23℃及び相対湿度65%RHの環境下でアルミニウム板に、2kgローラーを使用し一往復させることで圧着させ、温度23℃及び相対湿度50%RHの環境下に1時間静置した後に測定される剥離速度300mm/minにおける180°引き剥がし接着力が12N/20mm以上の粘着剤層である。前記特定の粘着剤層を使用することによって、解体時に一定の力を加えることで発泡体基材の層間割れを実現でき、かつ優れた耐衝撃性を備えた両面粘着テープを得ることができる。 [Adhesive layer]
The adhesive layer which the double-sided adhesive tape of this invention has is provided in the front and back (both surfaces) of a foam base material. At least one of the pressure-sensitive adhesive layers provided on each surface, preferably both pressure-sensitive adhesive layers are formed by forming a pressure-sensitive adhesive tape formed by providing a 25 μm-thick pressure-sensitive adhesive layer on a 25 μm-thick polyethylene terephthalate substrate. Measured after pressure-bonding to an aluminum plate by reciprocating once using an aluminum plate in an environment of ℃ and relative humidity of 65% RH, and standing for 1 hour in an environment of temperature of 23 ℃ and relative humidity of 50% RH. It is a pressure-sensitive adhesive layer having a 180 ° peeling adhesive strength of 12 N / 20 mm or more at a peeling speed of 300 mm / min. By using the specific pressure-sensitive adhesive layer, it is possible to obtain a double-sided pressure-sensitive adhesive tape that can realize interlaminar cracking of the foam base material by applying a certain force at the time of disassembly and that has excellent impact resistance.
サンプル注入量:100μl
溶離液:THF
流速:1.0ml/分
測定温度:40℃
本カラム:TSKgel GMHHR-H(20)2本
ガードカラム:TSKgel HXL-H
検出器:示差屈折計
スタンダードポリスチレン分子量:1万~2000万(東ソー株式会社製) Sample concentration: 0.5% by mass (tetrahydrofuran solution)
Sample injection volume: 100 μl
Eluent: THF
Flow rate: 1.0 ml / min Measurement temperature: 40 ° C
This column: TSKgel GMHHR-H (20) 2 Guard column: TSKgel HXL-H
Detector: differential refractometer Standard polystyrene molecular weight: 10,000 to 20 million (manufactured by Tosoh Corporation)
本発明の両面粘着テープは、例えば、発泡体基材に直接、または、発泡体基材上に積層された他の層の表面に、粘着剤を塗布して乾燥させる直写法、剥離シートに粘着剤を塗布して乾燥させた後、発泡体基材や他の層表面に貼り合せる転写法によって製造することができる。 [Double-sided adhesive tape]
The double-sided pressure-sensitive adhesive tape of the present invention is, for example, a direct copy method in which an adhesive is applied and dried directly on a foam base material or on the surface of another layer laminated on the foam base material, and sticks to a release sheet. After the agent is applied and dried, it can be produced by a transfer method in which it is bonded to the surface of the foam substrate or other layer.
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート97.97質量部、アクリル酸2.0質量部、4-ヒドロキブチルアクリレート0.03質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が200万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (A))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 97.97 parts by mass of n-butyl acrylate, 2.0 parts by mass of acrylic acid, 0.03 parts by mass of 4-hydroxybutyl acrylate Part by weight, 0.1 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator was dissolved in 100 parts by mass of ethyl acetate and polymerized at 70 ° C. for 12 hours to obtain a weight average molecular weight of 2 million ( An ethyl acetate solution of an acrylic polymer (in terms of polystyrene) was obtained.
厚さ25μmのポリエチレンテレフタレート基材に、乾燥後の粘着剤層の厚さが25μmとなるように前記粘着剤組成物(A)を塗工し、80℃で3分乾燥した後、40℃の環境下で48時間熟成することによって粘着テープを得た。 [Adhesive strength of adhesive layer by 180 ° peeling]
The pressure-sensitive adhesive composition (A) was applied to a polyethylene terephthalate substrate having a thickness of 25 μm so that the thickness of the pressure-sensitive adhesive layer after drying was 25 μm, dried at 80 ° C. for 3 minutes, and then heated to 40 ° C. An adhesive tape was obtained by aging in an environment for 48 hours.
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート93.4質量部、アクリル酸3.5質量部、酢酸ビニル3質量部、2-ヒドロキシエチルアクリレート0.1質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が160万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (B))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 93.4 parts by mass of n-butyl acrylate, 3.5 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, 2-hydroxy By dissolving 0.1 part by weight of ethyl acrylate and 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator in 100 parts by weight of ethyl acetate and polymerizing at 70 ° C. for 12 hours, An ethyl acetate solution of an acrylic polymer having an average molecular weight of 1,600,000 (polystyrene conversion) was obtained.
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート93.4質量部、アクリル酸3.5質量部、酢酸ビニル3質量部、2-ヒドロキシエチルアクリレート0.1質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が160万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (C))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 93.4 parts by mass of n-butyl acrylate, 3.5 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, 2-hydroxy By dissolving 0.1 part by weight of ethyl acrylate and 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator in 100 parts by weight of ethyl acetate and polymerizing at 70 ° C. for 12 hours, An ethyl acetate solution of an acrylic polymer having an average molecular weight of 1,600,000 (polystyrene conversion) was obtained.
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート44.94質量部、2-エチルヘキシルアクリレート50質量部、酢酸ビニル3質量部、アクリル酸2質量部、4-ヒドロキシブチルアクリレート0.06質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が120万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (D))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 44.94 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of vinyl acetate,
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート63.4質量部、2-エチルヘキシルアクリレート30質量部、アクリル酸3質量部、酢酸ビニル3.5質量部、2-ヒドロキシエチルアクリレート0.1質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が140万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (E))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 63.4 parts by mass of n-butyl acrylate, 30 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of acrylic acid, 3 vinyl acetates 0.5 part by mass, 0.1 part by mass of 2-hydroxyethyl acrylate, 0.1 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator were dissolved in 100 parts by mass of ethyl acetate, and the mixture was dissolved at 70 ° C. By polymerizing for 12 hours, an ethyl acetate solution of an acrylic polymer having a weight average molecular weight of 1.4 million (in terms of polystyrene) was obtained.
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート44.94質量部、2-エチルヘキシルアクリレート50質量部、酢酸ビニル3質量部、アクリル酸2質量部、4-ヒドロキシブチルアクリレート0.06質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が120万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (F))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 44.94 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of vinyl acetate,
攪拌機、還流冷却器、温度計、滴下漏斗および窒素ガス導入口を備えた反応容器に、n-ブチルアクリレート93.4質量部、アクリル酸3.5質量部、酢酸ビニル3質量部、2-ヒドロキシエチルアクリレート0.1質量部、重合開始剤として2、2’-アゾビスイソブチロニトリル0.1質量部を、酢酸エチル100質量部に溶解し、70℃で12時間重合させることによって、重量平均分子量が160万(ポリスチレン換算)のアクリル系重合体の酢酸エチル溶液を得た。 (Preparation of pressure-sensitive adhesive composition (G))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 93.4 parts by mass of n-butyl acrylate, 3.5 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, 2-hydroxy By dissolving 0.1 part by weight of ethyl acrylate and 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator in 100 parts by weight of ethyl acetate and polymerizing at 70 ° C. for 12 hours, An ethyl acetate solution of an acrylic polymer having an average molecular weight of 1,600,000 (polystyrene conversion) was obtained.
前記粘着剤組成物(A)を厚さ75μmのポリエチレンテレフタレートフィルム(PETフィルム)の剥離処理面に、乾燥後の厚さが25μmとなるように塗工し、80℃で3分間乾燥させることによって粘着剤層を形成した。前記粘着剤層のゲル分率は42.5質量%であった。 (Example 1)
By coating the pressure-sensitive adhesive composition (A) on the peel-treated surface of a 75 μm-thick polyethylene terephthalate film (PET film) to a thickness of 25 μm after drying, and drying at 80 ° C. for 3 minutes. An adhesive layer was formed. The gel fraction of the pressure-sensitive adhesive layer was 42.5% by mass.
粘着剤層の乾燥後の厚さを25μmから15μmに変更したこと以外は、実施例1と同様の方法で厚さ130μmの両面粘着テープを得た。 (Example 2)
A double-sided pressure-sensitive adhesive tape having a thickness of 130 μm was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 25 μm to 15 μm.
粘着剤層の乾燥後の厚さを25μmから50μmに変更したこと以外は、実施例1と同様の方法で厚さ200μmの両面粘着テープを得た。 (Example 3)
A double-sided pressure-sensitive adhesive tape having a thickness of 200 μm was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 25 μm to 50 μm.
黒色ポリオレフィン系発泡体(1)の代わりに、黒色ポリオレフィン系発泡体(2)(厚さ:80μm、密度0.40g/cm3、層間強度10.2N/cm、25%圧縮強度:92kPa、流れ方向の引張強さ:1062N/cm2、幅方向の引張強さ:962N/cm2、である積水化学工業株式会社製の発泡体の表面をコロナ処理で濡れ指数54mN/mとしたもの)を用いること、及び、粘着剤層の乾燥後の厚さを25μmから15μmに変更したこと以外は、実施例1と同様の方法で厚さ110μmの両面粘着テープを得た。 Example 4
Instead of the black polyolefin foam (1), the black polyolefin foam (2) (thickness: 80 μm, density 0.40 g / cm 3 , interlayer strength 10.2 N / cm, 25% compression strength: 92 kPa, flow The tensile strength in the direction: 1062 N / cm 2 , the tensile strength in the width direction: 962 N / cm 2 , and the surface of the foam made by Sekisui Chemical Co., Ltd. was subjected to corona treatment to a wetting index of 54 mN / m) A double-sided pressure-sensitive adhesive tape having a thickness of 110 μm was obtained in the same manner as in Example 1 except that the thickness after drying of the pressure-sensitive adhesive layer was changed from 25 μm to 15 μm.
黒色ポリオレフィン系発泡体(1)の代わりに黒色ポリオレフィン系発泡体(3)(厚さ:100μm、密度0.45g/cm3、層間強度16.2N/cm、25%圧縮強度:190kPa、流れ方向の引張強さ:964N/cm2、幅方向の引張強さ:861N/cm2、である積水化学工業株式会社製の発泡体の表面をコロナ処理で濡れ指数54mN/mとしたもの)を用いたこと以外は、実施例1と同様の方法で、厚さ150μmの両面粘着テープを得た。 (Example 5)
Black polyolefin foam (3) instead of black polyolefin foam (1) (thickness: 100 μm, density 0.45 g / cm 3 , interlayer strength 16.2 N / cm, 25% compressive strength: 190 kPa, flow direction The surface of the foam made by Sekisui Chemical Co., Ltd. having a tensile strength of 964 N / cm 2 and a width direction tensile strength of 861 N / cm 2 is obtained by corona treatment with a wetting index of 54 mN / m) A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that it was not.
粘着剤層の乾燥後の厚さを15μmから50μmに変更したこと以外は、実施例5と同様の方法で厚さ200μmの両面粘着テープを得た。 (Example 6)
A double-sided pressure-sensitive adhesive tape having a thickness of 200 μm was obtained in the same manner as in Example 5 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 μm to 50 μm.
黒色ポリオレフィン系発泡体(1)の代わりに黒色ポリオレフィン系発泡体(4)(厚さ:140μm、密度0.40g/cm3、層間強度19.1N/cm、25%圧縮強度:130kPa、流れ方向の引張強さ:994N/cm2、幅方向の引張強さ:713N/cm2、である積水化学工業株式会社製の発泡体の表面をコロナ処理で濡れ指数54mN/mとしたもの)を用いること、及び、粘着剤層の乾燥後の厚さを15μmから30μmにしたこと以外は、実施例1と同様の方法で厚さ200μmの両面粘着テープを得た。 (Example 7)
Black polyolefin foam (4) instead of black polyolefin foam (1) (thickness: 140 μm, density 0.40 g / cm 3 , interlayer strength 19.1 N / cm, 25% compressive strength: 130 kPa, flow direction The surface of the foam made by Sekisui Chemical Co., Ltd. with a tensile strength of 994 N / cm 2 and a width direction tensile strength of 713 N / cm 2 was used to obtain a wet index of 54 mN / m by corona treatment. A double-sided pressure-sensitive adhesive tape having a thickness of 200 μm was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 μm to 30 μm.
粘着剤層の乾燥後の厚さを30μmから55μmに変更したこと以外は、実施例7と同様の方法で厚さ250μmの両面粘着テープを得た。 (Example 8)
A double-sided pressure-sensitive adhesive tape having a thickness of 250 μm was obtained in the same manner as in Example 7, except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 30 μm to 55 μm.
粘着剤層の乾燥後の厚さを30μmから80μmに変更したこと以外は、実施例7と同様の方法で厚さ300μmの両面粘着テープを得た。 Example 9
A double-sided pressure-sensitive adhesive tape having a thickness of 300 μm was obtained in the same manner as in Example 7, except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 30 μm to 80 μm.
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(B)を使用すること以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た(粘着剤層のゲル分率40質量%)。 (Example 10)
A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (B) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 40% by mass).
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(C)を使用すること以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た(粘着剤層のゲル分率43質量%)。 (Example 11)
A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (C) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 43% by mass).
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(D)を使用すること以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た(粘着剤層のゲル分率25質量%)。 Example 12
A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (D) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 25% by mass).
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(E)を使用すること以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た(粘着剤層のゲル分率39質量%)。 (Example 13)
A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (E) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 39% by mass).
黒色ポリオレフィン系発泡体(1)の代わりに黒色ポリオレフィン系発泡体(5)(厚さ:100μm、密度0.33g/cm3、層間強度8.9N/cm、25%圧縮強度:70kPa、流れ方向の引張強さ:799N/cm2、幅方向の引張強さ:627N/cm2、である積水化学工業株式会社製の発泡体の表面をコロナ処理で濡れ指数54mN/mとしたもの)を用いたこと以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た。 (Comparative Example 1)
Black polyolefin foam (5) instead of black polyolefin foam (1) (thickness: 100 μm, density 0.33 g / cm 3 , interlayer strength 8.9 N / cm, 25% compressive strength: 70 kPa, flow direction The surface of the foam made by Sekisui Chemical Co., Ltd. having a tensile strength of 799 N / cm 2 and a width direction tensile strength of 627 N / cm 2 is obtained by corona treatment with a wetting index of 54 mN / m. A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1, except that it was not.
黒色ポリオレフィン系発泡体(1)の代わりに黒色ポリオレフィン系発泡体(6)(厚さ:100μm、密度0.50g/cm3、層間強度13.6N/cm、25%圧縮強度:270kPa、流れ方向の引張強さ:1456N/cm2、幅方向の引張強さ:956N/cm2、である積水化学工業株式会社製の発泡体の表面をコロナ処理で濡れ指数54mN/mとしたもの)を用いたこと以外は、実施例1と同様の方法で、厚さ150μmの両面粘着テープを得た。 (Comparative Example 2)
Black polyolefin foam (6) instead of black polyolefin foam (1) (thickness: 100 μm, density 0.50 g / cm 3 , interlayer strength 13.6 N / cm, 25% compressive strength: 270 kPa, flow direction The surface of the foam made by Sekisui Chemical Co., Ltd. having a tensile strength of 1456 N / cm 2 and a tensile strength in the width direction of 956 N / cm 2 is obtained by corona treatment with a wetting index of 54 mN / m) A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that it was not.
粘着剤層の乾燥後の厚さを15μmから50μmに変更したこと以外は、比較例2と同様にして厚さ200μmの両面粘着テープを得た。 (Comparative Example 3)
A double-sided pressure-sensitive adhesive tape having a thickness of 200 μm was obtained in the same manner as in Comparative Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying was changed from 15 μm to 50 μm.
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(F)を使用すること以外は、実施例1と同様の方法で厚さ150μmの両面粘着テープを得た(粘着剤層のゲル分率38質量%)。 (Comparative Example 4)
A double-sided pressure-sensitive adhesive tape having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (F) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 38% by mass).
前記粘着剤組成物(A)の代わりに、前記粘着剤組成物(G)を使用すること以外は、実施例7と同様の方法で厚さ200μmの両面粘着テープを得た(粘着剤層のゲル分率48質量%)。 (Comparative Example 5)
A double-sided pressure-sensitive adhesive tape having a thickness of 200 μm was obtained in the same manner as in Example 7 except that the pressure-sensitive adhesive composition (G) was used instead of the pressure-sensitive adhesive composition (A) (the pressure-sensitive adhesive layer). Gel fraction 48% by mass).
発泡体基材の厚さは、尾崎製作所製のダイヤルシクネスゲージG型を用いて測定した。粘着テープの厚さは、剥離フィルムを剥がしたものの厚さを、ダイヤルシクネスゲージG型を用いて測定した。 [Foam substrate and adhesive tape thickness]
The thickness of the foam base material was measured using a dial series gauge G type manufactured by Ozaki Seisakusho. The thickness of the pressure-sensitive adhesive tape was measured by using a dial thickness gauge G type after peeling the release film.
発泡体基材の密度は、JISK6767に準じて測定した。具体的には、4cm×5cmの長方形に切断した発泡体基材を15cm3分用意し、その質量を測定して密度を求めた。 [Density of foam substrate]
The density of the foam substrate was measured according to JISK6767. Specifically, a foam base material cut into a 4 cm × 5 cm rectangle was prepared for 15 cm 3 minutes, and the mass was measured to determine the density.
発泡体基材の両面に、厚さ50μmの強粘着性(下記高速剥離試験時に被着体および発泡体基材から剥離しないもの)の粘着剤層を1枚ずつ貼り合わせたものを、40℃で48時間熟成することによって、層間強度測定用の両面粘着テープを作成した。 [Interlayer strength of foam substrate]
What adhered the adhesive layer of the strong adhesiveness (those which does not peel from a to-be-adhered body and a foam base material at the time of the following high-speed peeling test) one sheet each on both surfaces of a foam base material is 40 degreeC. Was aged for 48 hours to prepare a double-sided pressure-sensitive adhesive tape for measuring interlayer strength.
発泡体基材の流れ方向と幅方向の引張強さは、JISK6767に準じて測定した。標線長さ2cm、幅1cmのサンプルを、テンシロン引張試験機を用い、23℃及び相対湿度50%RHの環境下、引張速度300mm/minの測定条件で測定した。得られた測定値の最大強度がサンプルの引張強度である。 [Tensile strength of foam substrate]
The tensile strength in the flow direction and width direction of the foam substrate was measured according to JISK6767. A sample having a marked line length of 2 cm and a width of 1 cm was measured using a Tensilon tensile tester in an environment of 23 ° C. and a relative humidity of 50% RH under measurement conditions of a tensile speed of 300 mm / min. The maximum strength of the measured value obtained is the tensile strength of the sample.
発泡体基材の25%圧縮強度は、JISK6767に準じて測定した。25角に切断した試料を厚さ約10mmになるまで重ね合わせた。試料より大きな面積のステンレス板で試料をはさみ、23℃下で10mm/分の速度で試料を約2.5mm(もとの厚さの25%分)圧縮した時の強度を測定した。 [25% compressive strength of foam substrate]
The 25% compressive strength of the foam substrate was measured according to JISK6767. Samples cut into 25 squares were stacked to a thickness of about 10 mm. The sample was sandwiched between stainless plates having a larger area than the sample, and the strength was measured when the sample was compressed at about 25 mm (25% of the original thickness) at a rate of 10 mm / min at 23 ° C.
はじめに、発泡体基材を幅方法、流れ方向とも1cmに切断した。次に、切断した発泡体基材の切断面中央部分をデジタルマイクロスコープ(商品名「KH-7700」、HiROX社製)により、発泡体気泡部分を200倍に拡大したのち、発泡体基材の幅方向または流れ方向の断面を発泡体基材の切断面がその基材厚さ方向の全長を観察する。得られた拡大画像において、流れ方向または幅方向の拡大前の実際の長さが2mm分の切断面に存在する気泡の気泡径を全て測定し、その平均値から平均気泡径を算出した。任意の10カ所で測定した結果から平均気泡径を求めた。 [Measurement of average cell diameter of foam substrate]
First, the foam base material was cut into 1 cm in both the width method and the flow direction. Next, after the foam cell part was enlarged 200 times by a digital microscope (trade name “KH-7700”, manufactured by HiROX) at the center of the cut surface of the foam base material, The cross section in the width direction or the flow direction is observed on the entire length of the cut surface of the foam base material in the thickness direction of the base material. In the obtained enlarged image, all the bubble diameters of the bubbles existing on the cut surface having an actual length of 2 mm before expansion in the flow direction or the width direction were measured, and the average bubble diameter was calculated from the average value. The average bubble diameter was determined from the results of measurement at any 10 locations.
1)長さ2cm(発泡体基材の流れ方向)、幅1cmの試験片に加工した発泡体基材中芯の両面粘着テープを、縦2.5cm、横4.0cm、2mm厚のポリカーボネート板の中心に幅方向に2cmの間隔をあけて2枚貼付した。 [Easy disassembly]
1) Polycarbonate plate of 2.5 cm in length, 4.0 cm in width, and 2 mm in thickness on a double-sided adhesive tape with a foam base material core processed into a test piece having a length of 2 cm (flow direction of the foam base material) and a width of 1 cm Two sheets were affixed to the center of the sheet at an interval of 2 cm in the width direction.
1)厚さ2mm、外形50mm×50mmのアクリル板(三菱レイヨン(株)アクリライトL「商標名」、色相:透明)に、長さ40mm、幅5mmの2枚の両面粘着テープの弱粘着面を40mmの間隔をあけて平行に貼付(図1)したのち、厚さ2mm、外形150mm×100mmのABS板(住友ベークライト社製、タフエースR「商標名」色相:ナチュラル、シボなし、以下同じ)の中央部に貼付した(図2)。2kgローラーで1往復加圧したのち、23℃で1時間静置して試験片とした。 [Impact resistance test]
1) Weak adhesive surface of two double-sided adhesive tapes 40mm long and 5mm wide on an acrylic plate (Mitsubishi Rayon Co., Ltd. Acrylite L "trade name", hue: transparent) with a thickness of 2mm and an external dimension of 50mm x 50mm Are attached in parallel with an interval of 40 mm (Fig. 1), and then an ABS plate having a thickness of 2 mm and an outer shape of 150 mm x 100 mm (manufactured by Sumitomo Bakelite Co., Ltd., Tuface R "trade name" hue: natural, no grain, the same applies hereinafter) It stuck on the center part of (FIG. 2). After reciprocating pressure with a 2 kg roller, the test piece was left at 23 ° C. for 1 hour.
×:高さ60cm以下でテープの剥がれ又は破壊が生じた ○: No peeling or breaking of the tape after the test even at a height of 60 cm ×: peeling or breaking of the tape occurred at a height of 60 cm or less
2 アクリル板
3 ABS板
4 コの字型測定台
5 撃芯 DESCRIPTION OF
Claims (4)
- 発泡体基材の両面に粘着剤層を有する両面粘着テープであって、
前記発泡体基材が、密度0.45g/cm3以下、層間強度10N/cm以上の発泡体基材であり、
前記粘着剤層が、厚さ25μmのポリエチレンテレフタレート基材に厚さ25μmの粘着剤層を設けて形成した粘着テープを、温度23℃及び相対湿度65%RHの環境下でアルミニウム板に、2kgローラーを使用し一往復させることで圧着させ、温度23℃及び相対湿度50%RHの環境下に1時間静置した後に測定される剥離速度300mm/minにおける180°引き剥がし接着力が12N/20mm以上の粘着剤層であることを特徴とする両面粘着テープ。 A double-sided adhesive tape having an adhesive layer on both sides of a foam substrate,
The foam substrate is a foam substrate having a density of 0.45 g / cm 3 or less and an interlayer strength of 10 N / cm or more;
The pressure-sensitive adhesive layer is a 25-μm-thick polyethylene terephthalate base material provided with a 25-μm-thick pressure-sensitive adhesive layer on an aluminum plate at a temperature of 23 ° C. and a relative humidity of 65% RH. The adhesive strength is 12 N / 20 mm or more when peeled by 180 ° at a peeling speed of 300 mm / min, measured after leaving for 1 hour in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH. A double-sided pressure-sensitive adhesive tape characterized by being an adhesive layer. - 総厚さが300μm以下である請求項1に記載の両面粘着テープ。 The double-sided pressure-sensitive adhesive tape according to claim 1, having a total thickness of 300 µm or less.
- 前記発泡体基材の引張強さが、500N/cm2~1300N/cm2である請求項1に記載の両面粘着テープ。 The tensile strength of the foam substrate is double-sided adhesive tape according to claim 1 which is 500N / cm 2 ~ 1300N / cm 2.
- 電子機器を構成する部品の固定に使用される請求項1に記載の両面粘着テープ。 The double-sided pressure-sensitive adhesive tape according to claim 1, which is used for fixing components constituting an electronic device.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480018812.7A CN105073933B (en) | 2013-03-29 | 2014-03-18 | Double-faced adhesive tape |
JP2014537417A JP6058016B2 (en) | 2013-03-29 | 2014-03-18 | Double-sided adhesive tape |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-072533 | 2013-03-29 | ||
JP2013072533 | 2013-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014156816A1 true WO2014156816A1 (en) | 2014-10-02 |
Family
ID=51623796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/057287 WO2014156816A1 (en) | 2013-03-29 | 2014-03-18 | Double-sided adhesive tape |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6058016B2 (en) |
CN (1) | CN105073933B (en) |
TW (1) | TWI602898B (en) |
WO (1) | WO2014156816A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015120876A (en) * | 2013-11-22 | 2015-07-02 | 日東電工株式会社 | Double-sided adhesive sheet |
WO2016035747A1 (en) * | 2014-09-02 | 2016-03-10 | 積水化学工業株式会社 | Double-sided adhesive tape for portable electronic device |
JP2016079361A (en) * | 2014-10-22 | 2016-05-16 | Dic株式会社 | Adhesive tape, article obtained by using adhesive tape and decomposition method of article |
JP2016089145A (en) * | 2014-10-31 | 2016-05-23 | 積水化学工業株式会社 | Adhesive tape |
JP2016098259A (en) * | 2014-11-18 | 2016-05-30 | 積水化学工業株式会社 | Double sided adhesive tape |
WO2019043810A1 (en) | 2017-08-30 | 2019-03-07 | 株式会社寺岡製作所 | Adhesive tape |
WO2020175368A1 (en) * | 2019-02-25 | 2020-09-03 | 積水化学工業株式会社 | Dual-sided pressure-sensitive adhesive tape, electronic apparatus component, and electronic apparatus |
CN112011280A (en) * | 2020-08-31 | 2020-12-01 | 辛格顿(常州)新材料科技有限公司 | Manufacturing and laminating process of waterproof flame-retardant foam |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112143396A (en) * | 2013-11-22 | 2020-12-29 | 日东电工株式会社 | Double-sided adhesive sheet |
KR102292340B1 (en) * | 2013-12-25 | 2021-08-24 | 디아이씨 가부시끼가이샤 | Double-sided adhesive tape and electronic device |
CN108307640B (en) * | 2015-04-21 | 2021-10-26 | 株式会社寺冈制作所 | Adhesive sheet |
KR102645230B1 (en) * | 2017-03-15 | 2024-03-07 | 세키스이가가쿠 고교가부시키가이샤 | double sided adhesive tape |
TWI804497B (en) * | 2017-06-26 | 2023-06-11 | 日商迪愛生股份有限公司 | Adhesive tape and method for peeling adhesive tape from adherend |
JP7430513B2 (en) * | 2019-10-30 | 2024-02-13 | 日東電工株式会社 | double sided adhesive tape |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5710671A (en) * | 1980-06-20 | 1982-01-20 | Nitto Electric Ind Co Ltd | Fixing method of exterior trim material on car body surface |
JPH0715748U (en) * | 1993-08-20 | 1995-03-17 | 東洋ケミテック株式会社 | Adhesive sheet |
JP2004323842A (en) * | 2003-04-11 | 2004-11-18 | Sekisui Chem Co Ltd | Crosslinked polyolefin resin foamed sheet and pressure-sensitive adhesive tape |
JP2007262320A (en) * | 2006-03-29 | 2007-10-11 | Asahi Glass Co Ltd | Double-sided pressure sensitive adhesive sheet or tape for glass |
JP2009108314A (en) * | 2007-10-12 | 2009-05-21 | Dic Corp | Water-proofing double-sided adhesive tape |
JP2010155969A (en) * | 2008-12-04 | 2010-07-15 | Nitto Denko Corp | Double-faced pressure-sensitive adhesive tape |
JP2010215906A (en) * | 2009-02-20 | 2010-09-30 | Sekisui Chem Co Ltd | Adhesive sheet for use in electronic device |
JP2010260880A (en) * | 2009-04-09 | 2010-11-18 | Dic Corp | Double-sided adhesive tape |
JP2013040329A (en) * | 2011-07-15 | 2013-02-28 | Nitto Denko Corp | Double-sided adhesive sheet |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101181335B1 (en) * | 2009-04-09 | 2012-09-11 | 디아이씨 가부시끼가이샤 | Double sided pressure sensitive adhesive tape |
-
2014
- 2014-03-18 JP JP2014537417A patent/JP6058016B2/en active Active
- 2014-03-18 CN CN201480018812.7A patent/CN105073933B/en active Active
- 2014-03-18 WO PCT/JP2014/057287 patent/WO2014156816A1/en active Application Filing
- 2014-03-26 TW TW103111166A patent/TWI602898B/en active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5710671A (en) * | 1980-06-20 | 1982-01-20 | Nitto Electric Ind Co Ltd | Fixing method of exterior trim material on car body surface |
JPH0715748U (en) * | 1993-08-20 | 1995-03-17 | 東洋ケミテック株式会社 | Adhesive sheet |
JP2004323842A (en) * | 2003-04-11 | 2004-11-18 | Sekisui Chem Co Ltd | Crosslinked polyolefin resin foamed sheet and pressure-sensitive adhesive tape |
JP2007262320A (en) * | 2006-03-29 | 2007-10-11 | Asahi Glass Co Ltd | Double-sided pressure sensitive adhesive sheet or tape for glass |
JP2009108314A (en) * | 2007-10-12 | 2009-05-21 | Dic Corp | Water-proofing double-sided adhesive tape |
JP2010155969A (en) * | 2008-12-04 | 2010-07-15 | Nitto Denko Corp | Double-faced pressure-sensitive adhesive tape |
JP2010215906A (en) * | 2009-02-20 | 2010-09-30 | Sekisui Chem Co Ltd | Adhesive sheet for use in electronic device |
JP2010260880A (en) * | 2009-04-09 | 2010-11-18 | Dic Corp | Double-sided adhesive tape |
JP2013040329A (en) * | 2011-07-15 | 2013-02-28 | Nitto Denko Corp | Double-sided adhesive sheet |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015120876A (en) * | 2013-11-22 | 2015-07-02 | 日東電工株式会社 | Double-sided adhesive sheet |
JP2018193557A (en) * | 2013-11-22 | 2018-12-06 | 日東電工株式会社 | Double-sided adhesive sheet |
WO2016035747A1 (en) * | 2014-09-02 | 2016-03-10 | 積水化学工業株式会社 | Double-sided adhesive tape for portable electronic device |
JP2016079361A (en) * | 2014-10-22 | 2016-05-16 | Dic株式会社 | Adhesive tape, article obtained by using adhesive tape and decomposition method of article |
JP2016089145A (en) * | 2014-10-31 | 2016-05-23 | 積水化学工業株式会社 | Adhesive tape |
JP2016098259A (en) * | 2014-11-18 | 2016-05-30 | 積水化学工業株式会社 | Double sided adhesive tape |
WO2019043810A1 (en) | 2017-08-30 | 2019-03-07 | 株式会社寺岡製作所 | Adhesive tape |
US11286406B2 (en) | 2017-08-30 | 2022-03-29 | Teraoka Seisakusho Co., Ltd. | Adhesive tape |
WO2020175368A1 (en) * | 2019-02-25 | 2020-09-03 | 積水化学工業株式会社 | Dual-sided pressure-sensitive adhesive tape, electronic apparatus component, and electronic apparatus |
JPWO2020175368A1 (en) * | 2019-02-25 | 2021-09-27 | 積水化学工業株式会社 | Double-sided adhesive tape, electronic equipment parts and electronic equipment |
JP7044878B2 (en) | 2019-02-25 | 2022-03-30 | 積水化学工業株式会社 | Double-sided adhesive tape, electronic device parts and electronic devices |
CN112011280A (en) * | 2020-08-31 | 2020-12-01 | 辛格顿(常州)新材料科技有限公司 | Manufacturing and laminating process of waterproof flame-retardant foam |
Also Published As
Publication number | Publication date |
---|---|
JP6058016B2 (en) | 2017-01-11 |
TWI602898B (en) | 2017-10-21 |
CN105073933B (en) | 2018-03-30 |
CN105073933A (en) | 2015-11-18 |
TW201508044A (en) | 2015-03-01 |
JPWO2014156816A1 (en) | 2017-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6058016B2 (en) | Double-sided adhesive tape | |
JP5700180B1 (en) | Double-sided adhesive tape | |
JP5299596B1 (en) | Adhesive tape | |
KR101653985B1 (en) | Pressure-sensitive adhesive tape | |
JP5477517B1 (en) | Adhesive tape | |
JP5517015B1 (en) | Adhesive tape | |
JP5875031B2 (en) | Double-sided adhesive tape and electronic equipment | |
JP5510763B1 (en) | Adhesive tape | |
JP5700178B2 (en) | Adhesive tape and electronic equipment | |
JP6314341B2 (en) | Double-sided adhesive tape and articles | |
JP6326589B2 (en) | Double-sided adhesive tape and articles | |
WO2015029834A1 (en) | Adhesive sheet, article, and electronic device | |
JP2015098554A (en) | Waterproof tape | |
JP6269034B2 (en) | Double-sided adhesive tape |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480018812.7 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2014537417 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14773490 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14773490 Country of ref document: EP Kind code of ref document: A1 |