WO2017131082A1 - 両面粘着テープ - Google Patents
両面粘着テープ Download PDFInfo
- Publication number
- WO2017131082A1 WO2017131082A1 PCT/JP2017/002712 JP2017002712W WO2017131082A1 WO 2017131082 A1 WO2017131082 A1 WO 2017131082A1 JP 2017002712 W JP2017002712 W JP 2017002712W WO 2017131082 A1 WO2017131082 A1 WO 2017131082A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- double
- adhesive tape
- weight
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
Definitions
- the present invention relates to a double-sided pressure-sensitive adhesive tape that is thin but excellent in shock absorption and removability.
- Mobile electronic devices such as mobile phones and personal information terminals (Personal Digital Assistants, PDAs) are designed so that they do not come off or break even if an impact is applied in consideration of falling from the user's hand to the foot.
- PDAs Personal Digital Assistants
- Fixed arrangements or device body designs are being considered. Therefore, a double-sided pressure-sensitive adhesive tape that is used for fixing the component to the main body of the device is desired to prevent the component from coming off even when an impact is applied, and not to apply a strong shock to the component. ing.
- a double-sided pressure-sensitive adhesive tape having a base material made of a polyolefin foam has been studied as an impact absorbing tape for fixing a component constituting a portable electronic device to the device body.
- an acrylic pressure-sensitive adhesive layer is laminated and integrated on at least one surface of a base material layer, and the base material layer has a specific cross-linking degree and a foam aspect ratio.
- a shock absorbing tape is described.
- double-sided pressure-sensitive adhesive tapes are also used for fixing automobile members (for example, in-vehicle panels) to the automobile body, and as such double-sided pressure-sensitive adhesive tapes, a base made of a polyolefin foam having excellent shock absorbing performance is also used. A double-sided adhesive tape having a material is used.
- the double-sided adhesive tape used is also required to be thinner.
- the double-sided pressure-sensitive adhesive tape having a base material made of a conventional foam is thinned, there is a problem that the strength of the base material is lowered and the tape is easily delaminated. Further, when the strength of the substrate is lowered, the tape is excessively stretched when the tape is pulled, and therefore there is a problem that the removability is poor.
- An object of the present invention is to provide a double-sided pressure-sensitive adhesive tape that is thin but excellent in impact absorption and removability.
- the present invention is a double-sided pressure-sensitive adhesive tape having an acrylic pressure-sensitive adhesive layer on both sides of a base material made of polyolefin foam, wherein the base material made of the polyolefin foam has a thickness of 50 to 120 ⁇ m, and is made of the polyolefin foam.
- the double-sided pressure-sensitive adhesive tape has an average cell diameter in the MD direction and TD direction of the substrate of 30 ⁇ m or more and 70 ⁇ m or less, and the total thickness of the double-sided pressure-sensitive adhesive tape is 80 to 150 ⁇ m.
- the present inventors have determined the average cell diameter of the base material in the double-sided pressure-sensitive adhesive tape having an acrylic pressure-sensitive adhesive layer on both surfaces of the base material made of polyolefin foam. It has been found that the strength can be ensured even when the substrate is made thinner by making it smaller than the conventional substrate. As a result, the present inventors have found that a double-sided pressure-sensitive adhesive tape that is thin and excellent in impact absorption and removability can be obtained despite having a base material made of foam, and has completed the present invention.
- the double-sided pressure-sensitive adhesive tape of the present invention has a base material (hereinafter also simply referred to as “base material”) made of a polyolefin foam.
- base material a base material
- a polyolefin foam As a base material, it is possible to impart impact absorbability to the double-sided pressure-sensitive adhesive tape obtained.
- the polyolefin foam is not particularly limited as long as it is a polyolefin foam that satisfies the average cell diameter in the MD direction and TD direction, which will be described later, and examples thereof include a polyethylene foam, a polypropylene foam, and an ethylene-propylene foam. It is done. Among these, a polyethylene foam is preferable.
- the base material has a lower limit of 50 ⁇ m and an upper limit of 120 ⁇ m.
- the double-sided pressure-sensitive adhesive tape of the present invention has a base material made of a foam, the strength of the base material can be ensured even when the thickness is thin, so that delamination does not easily occur even if the thickness is reduced. Also excellent in removability.
- the minimum with the preferable thickness of the said base material is 60 micrometers, and a preferable upper limit is 100 micrometers.
- the polyolefin foam has an average cell diameter in the MD direction and TD direction of 30 ⁇ m or more and 70 ⁇ m or less.
- the polyolefin foam has a small average cell diameter of 30 ⁇ m or more and 70 ⁇ m or less, so that the strength can be maintained even when the substrate is thinned, while both impact absorption and removability are compatible.
- a thin double-sided adhesive tape can be obtained.
- a preferable lower limit of the average cell diameter of the polyolefin foam is 35 ⁇ m, and a more preferable lower limit is 40 ⁇ m.
- the preferable upper limit of the average bubble diameter is 65 ⁇ m, and the more preferable upper limit is 55 ⁇ m.
- a method of reducing the average bubble diameter includes a method of pressurizing a resin before foaming.
- pressurizing the resin before foaming it is possible to suppress the growth of bubbles during foaming.
- the bubble diameter in MD direction and TD direction can be reduced as the stretch ratio in the MD direction and TD direction at the time of foaming is small, foaming is achieved by reducing the thickness of the resin by applying pressure before foaming. While suppressing the stretching at the time, the substrate can be made thin and the bubbles can be reduced.
- MD direction Machine Direction
- TD direction Transverse Direction
- the average cell diameter in the MD direction can be measured by the following method. First, a sample of polyolefin foam is cut into a 50 mm square, immersed in liquid nitrogen for 1 minute, and then cut along a plane parallel to the MD direction and the thickness direction with a razor blade. Next, using a digital microscope (for example, “VHX-900” manufactured by Keyence Co., Ltd.), a magnified photograph was taken at a magnification of 200 times, and all bubbles present on the cut surface having a length of 2 mm in the MD direction were MD. Measure the bubble size in the direction. The operation is repeated 5 times, and the average value of the bubble diameters in all MD directions is defined as the average bubble diameter in the MD direction.
- the average cell diameter in the TD direction can also be measured in the same manner except that the polyolefin foam sample is cut along a plane parallel to the TD direction and the thickness direction.
- the average bubble diameter in the MD direction and the average bubble diameter in the TD direction may be specified as follows. That is, first, in the polyolefin foam sample, one arbitrary direction perpendicular to the thickness direction is selected as the first direction, and the first direction and the direction perpendicular to the thickness direction are defined as the second direction. Next, a sample of the polyolefin foam is cut along a plane parallel to the first direction and the thickness direction, and the average cell diameter in the first direction is measured in the same manner as in the measurement method. The obtained average bubble diameter is treated as the average bubble diameter in the MD direction. Further, except that the polyolefin foam sample was cut along a plane parallel to the second direction and the thickness direction, the measurement was performed in the same manner as the measurement method described above, and the average cell diameter obtained was the average in the TD direction. Treat as bubble size.
- one or two bubbles in the polyolefin foam are included in the thickness direction of the polyolefin foam.
- one or two bubbles having the average cell diameter in the thickness direction in the base material it is easy to ensure strength even when the base material is thinned.
- the lower limit of the expansion ratio of the polyolefin foam is preferably 1.4 cm 3 / g and the upper limit is 2.0 cm 3 / g.
- the expansion ratio of the base material is 1.4 cm 3 / g or more, the flexibility and impact absorbability of the double-sided pressure-sensitive adhesive tape can be improved.
- the expansion ratio of the substrate is 2.0 cm 3 / g or less, the strength of the substrate is increased, delamination can be prevented, and a double-sided pressure-sensitive adhesive tape excellent in removability can be obtained.
- the expansion ratio can be calculated as the reciprocal of the density measured using an electronic hydrometer (for example, “ED120T” manufactured by Mirage Co., Ltd.) in accordance with JISK-6767.
- the base material which consists of a polyolefin foam whose average cell diameter of the said MD direction and TD direction is 30 micrometers or more and 70 micrometers or less can be manufactured by passing through the following processes, for example.
- a polyolefin resin composition made into a sheet by feeding a polyolefin resin, a pyrolytic foaming agent, and other additives to an extruder, melt-kneading, and extruding the sheet from the extruder. Obtaining step.
- the polyolefin foam can be produced by a method described in International Publication No. 2005/007731.
- the polyolefin-based resin examples include a polyethylene-based resin and a polypropylene-based resin, and among them, a polyethylene-based resin is preferable.
- the polyethylene resin may be an ethylene homopolymer, but is preferably an ethylene- ⁇ -olefin copolymer obtained by copolymerizing ethylene and a small amount of ⁇ -olefin.
- the polyethylene resin By using the polyethylene resin as a copolymer of ethylene and a small amount of ⁇ -olefin, the flexibility of the foam can be increased and the shock absorption can be further increased.
- the ethylene- ⁇ -olefin copolymers linear low density polyethylene is more preferable.
- Examples of the ⁇ -olefin in the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Can be mentioned. Of these, ⁇ -olefins having 4 to 10 carbon atoms are preferable.
- the preferable upper limit of the ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is 30% by weight, and the more preferable upper limit is 10% by weight.
- an ethylene-vinyl acetate copolymer is also preferable.
- the ethylene-vinyl acetate copolymer is usually a copolymer containing 50% by weight or more of structural units derived from ethylene.
- the polyethylene resin preferably has a low density from the viewpoint of enhancing the flexibility of the foam and enhancing the impact absorption.
- the density of the polyethylene resin is preferably from 0.920 g / cm 3 or less, more preferably 0.880 ⁇ 0.915g / cm 3, more preferably 0.885 ⁇ 0.910g / cm 3.
- the density is a value measured according to ASTM D792.
- Examples of the polypropylene resin used as a raw material for the polypropylene foam include a propylene homopolymer and a propylene- ⁇ -olefin copolymer containing 50% by weight or more of a structural unit derived from propylene. These may be used alone or in combination of two or more.
- Examples of the ⁇ -olefin in the propylene- ⁇ -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. It is done. Among these, ⁇ -olefins having 6 to 12 carbon atoms are preferable.
- the polyolefin resin in the polyolefin resin composition is a polyethylene resin polymerized by using a metallocene compound, a Ziegler-Natta compound, a chromium oxide compound or the like as a catalyst from the viewpoint of improving flexibility and impact absorption.
- the metallocene compound is preferably a compound such as a bis (cyclopentadienyl) metal complex having a structure in which a transition metal is sandwiched between ⁇ -electron unsaturated compounds.
- a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, and platinum has one or more cyclopentadienyl rings or analogs thereof as a ligand (ligand).
- ligand ligand
- the polymer synthesized using the above metallocene compound has high uniformity in molecular weight, molecular weight distribution, composition, composition distribution, etc., and thus when a sheet containing a polymer synthesized using the above metallocene compound is crosslinked. In this case, the crosslinking proceeds uniformly. Since the uniformly crosslinked sheet is easily stretched uniformly, the thickness of the polyolefin foam is easily uniformed.
- the ligand examples include cyclic compounds such as a cyclopentadienyl ring and an indenyl ring.
- the cyclic compound may have a substituent such as a hydrocarbon group, a substituted hydrocarbon group, or a hydrocarbon-substituted metalloid group.
- the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups.
- “various” means various isomers such as n-, sec-, tert-, iso- and the like.
- what polymerized the said cyclic compound as an oligomer may be used as a ligand.
- monovalent anion ligands such as chlorine and bromine, divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
- metallocene compound containing a tetravalent transition metal or a ligand examples include, for example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, Examples thereof include dimethylsilyltetramethylcyclopentadienyl-tert-butylamidozirconium dichloride.
- the said metallocene compound exhibits the effect
- cocatalyst include methylaluminoxane (MAO) and boron compounds.
- the use ratio of the cocatalyst to the metallocene compound is preferably 100,000 to 1,000,000 mole times, more preferably 50 to 5,000 mole times.
- the content is preferably 40% by weight or more of the total polyolefin resin, % By weight or more is more preferable, 60% by weight or more is more preferable, and 100% by weight is particularly preferable.
- the polyolefin foam is thin because the content of the polyethylene resin, ethylene-vinyl acetate copolymer, or mixture thereof obtained by using the metallocene compound as a catalyst is 40% by weight or more Even so, a high compressive strength can be obtained.
- the Ziegler-Natta compound is a triethylaluminum-titanium tetrachloride solid composite, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with various electron donors and electron acceptors.
- a method of combining a titanium composition, an organoaluminum compound and an aromatic carboxylic acid ester see JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907
- Method of supported catalyst in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide see JP-A-57-63310, JP-A-63-43915, JP-A-63-83116
- the said polyolefin resin composition may contain arbitrary components, such as resin other than the polyolefin resin mentioned above.
- gum are mentioned.
- the total content of these optional components is preferably less than that of the polyolefin resin. Specifically, the content is preferably 50 parts by weight or less and 100 parts by weight or less with respect to 100 parts by weight of the polyolefin resin. Is more preferable.
- the pyrolytic foaming agent is not particularly limited, and examples thereof include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, and among them, azodicarbonamide is preferable.
- the said thermal decomposition type foaming agent may be used independently and may be used in combination of 2 or more type.
- the content of the thermally decomposable foaming agent in the polyolefin resin composition is preferably 1 to 12 parts by weight and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the polyolefin resin.
- the content of the pyrolytic foaming agent is within the above range, the foamability of the polyolefin-based resin composition is improved, and it becomes easy to obtain a polyolefin foam having a desired foaming ratio, as well as tensile strength and compression. Recoverability can be improved.
- Examples of the additive include a decomposition temperature adjusting agent, a crosslinking aid, and an antioxidant.
- the said decomposition temperature regulator adjusts the surface state etc. of a foam by lowering
- Examples of the decomposition temperature adjusting agent include zinc oxide, zinc stearate, urea and the like.
- the content of the decomposition temperature adjusting agent with respect to 100 parts by weight of the polyolefin resin is preferably 0.01 to 5 parts by weight.
- the crosslinking aid is added to the polyolefin resin to reduce the amount of ionizing radiation to be irradiated in the step of crosslinking the polyolefin resin composition, which will be described later, and to cleave the resin molecules accompanying the irradiation of ionizing radiation. This is to prevent deterioration.
- a polyfunctional monomer etc. are mentioned, for example. Specifically, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, etc.
- the addition amount of the crosslinking aid is preferably 0.2 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and still more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin.
- the addition amount of the crosslinking aid is 0.2 parts by weight or more, a polyolefin foam having a desired degree of crosslinking can be stably obtained.
- the addition amount of the crosslinking aid is 10 parts by weight or less, the degree of crosslinking of the polyolefin foam can be easily controlled.
- the antioxidant is blended to prevent oxidative deterioration due to heat.
- examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol.
- the polyolefin resin composition is irradiated with ionizing radiation such as electron beam, ⁇ ray, ⁇ ray, and ⁇ ray. And a method in which an organic peroxide is blended in advance when the polyolefin resin composition is formed, and then the organic peroxide is decomposed by heating the polyolefin resin composition. These methods may be used alone or in combination of two or more. From the viewpoint of homogeneous crosslinking, a method of irradiating ionizing radiation is preferable.
- the dose of ionizing radiation in the method of irradiating with ionizing radiation is preferably adjusted so that the gel fraction is 5 to 45% by weight.
- a specific irradiation amount is preferably 0.5 to 20 Mrad, and more preferably 3 to 12 Mrad.
- the gel fraction (crosslinking degree) of a polyolefin-type resin composition can be measured as follows. That is, about 50 mg of a test piece is taken from the polyolefin foam, and the weight A (mg) of the test piece is precisely weighed. Next, this test piece was immersed in 30 cm 3 of xylene at 105 ° C.
- Examples of the organic peroxide in the method of previously blending an organic peroxide into the polyolefin resin composition include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1, Examples thereof include 1-bis (t-butylperoxy) cyclohexane. These may be used alone or in combination of two or more.
- the amount of the organic peroxide added is preferably 0.01 to 5 parts by weight and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the polyolefin resin.
- the amount of the organic peroxide is within the above range, the crosslinking of the polyolefin resin composition is likely to proceed, and the amount of the organic peroxide decomposition residue present in the resulting polyolefin foam is reduced. Can be suppressed.
- the foaming method of the polyolefin resin composition is not particularly limited.
- the method of heating the polyolefin resin composition with hot air the method of heating with infrared rays, or heating with a salt bath.
- a method of heating with an oil bath, etc. and these may be used in combination.
- the foaming of the polyolefin-based resin composition is not limited to an example using a pyrolytic foaming agent, and physical foaming with butane gas or the like may be used.
- the stretching may be performed after foaming the polyolefin resin composition to obtain a foam, or may be performed while foaming the polyolefin resin composition.
- the foam may be stretched after the cooled foam is heated again to a molten or softened state.
- the draw ratio in the MD direction of the polyolefin-based resin composition is preferably 1.1 to 3.0 times, and more preferably 1.7 to 2.8 times.
- the draw ratio in the MD direction of the polyolefin foam is preferably 1.1 to 3.0 times, and more preferably 1.7 to 2.8 times.
- the double-sided pressure-sensitive adhesive tape of the present invention has an acrylic pressure-sensitive adhesive layer on both sides of the substrate.
- the thickness of the acrylic pressure-sensitive adhesive layer the thickness of the single-sided acrylic pressure-sensitive adhesive layer is preferably 50 ⁇ m or less.
- the thickness of the acrylic pressure-sensitive adhesive layer is 50 ⁇ m or less, the impact resistance and shear adhesive strength of the double-sided pressure-sensitive adhesive tape can be compatible with the thinness of the double-sided pressure-sensitive adhesive tape.
- a more preferable upper limit of the acrylic pressure-sensitive adhesive layer is 30 ⁇ m.
- the minimum in particular of the thickness of the said acrylic adhesive layer is not restrict
- the acrylic copolymer constituting the acrylic pressure-sensitive adhesive layer is preferably obtained by copolymerizing a monomer mixture containing butyl acrylate and 2-ethylhexyl acrylate.
- the preferred content of butyl acrylate in the total monomer mixture is 40 to 80% by weight.
- the acrylic pressure-sensitive adhesive layer has appropriate softness and cohesion, and the shear pressure-sensitive adhesive force of the double-sided pressure-sensitive adhesive tape can be improved.
- the acrylic pressure-sensitive adhesive layer has an appropriate hardness, and the adhesive strength or tack is increased so that the shear adhesive strength of the double-sided adhesive tape can be improved.
- the preferred content of 2-ethylhexyl acrylate in the total monomer mixture is 10 to 40% by weight.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer is increased, and the shear adhesive strength of the double-sided pressure-sensitive adhesive tape can be improved.
- the acrylic pressure-sensitive adhesive layer has appropriate softness and cohesion, and the shear pressure-sensitive adhesive strength of the double-sided pressure-sensitive adhesive tape can be improved.
- the monomer mixture may contain other copolymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate as necessary.
- examples of other polymerizable monomers that can be copolymerized include, for example, carbon number of alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate.
- (Meth) acrylic acid alkyl ester having 1 to 3 carbon atoms such as (meth) acrylic acid alkyl ester, tridecyl methacrylate, stearyl (meth) acrylate, and the like, and (meth) acrylic acid hydroxyalkyl And functional monomers such as glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid and fumaric acid.
- the monomer mixture may be radically reacted in the presence of a polymerization initiator.
- a method of radical reaction of the monomer mixture that is, a polymerization method
- examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
- the said polymerization initiator is not specifically limited, For example, an organic peroxide, an azo compound, etc. are mentioned.
- organic peroxide examples include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5 -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples include isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxylaurate.
- the azo compound examples include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. These polymerization initiators may be used alone or in combination of two or more.
- a preferable minimum is 400,000 and a preferable upper limit is 2 million.
- the weight average molecular weight is 400,000 or more, the cohesive force of the acrylic pressure-sensitive adhesive layer is improved, and the shear adhesive force of the double-sided pressure-sensitive adhesive tape can be further increased.
- the weight average molecular weight is 2 million or less, the adhesive force of the acrylic pressure-sensitive adhesive layer is improved, and the shear adhesive force of the double-sided pressure-sensitive adhesive tape can be further increased.
- a more preferable lower limit of the weight average molecular weight is 500,000, and a more preferable upper limit is 1,500,000.
- a weight average molecular weight is a weight average molecular weight of standard polystyrene conversion by GPC (Gel Permeation Chromatography: gel permeation chromatography).
- the acrylic pressure-sensitive adhesive layer may contain a tackifier resin.
- tackifier resins include rosin ester resins, hydrogenated rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, alicyclic saturated hydrocarbon resins, C5 petroleum resins, and C9 resins. Examples include petroleum resins and C5-C9 copolymer petroleum resins. These tackifying resins may be used alone or in combination of two or more.
- content of the said tackifying resin is not specifically limited,
- the preferable minimum with respect to 100 weight part of said acrylic copolymers is 10 weight part, and a preferable upper limit is 60 weight part.
- the content of the tackifying resin is 10 parts by weight or more, the adhesive strength of the acrylic pressure-sensitive adhesive layer is improved, and the shear adhesive strength of the double-sided pressure-sensitive adhesive tape can be further increased.
- the content of the tackifying resin is 60 parts by weight or less, the acrylic pressure-sensitive adhesive layer has an appropriate hardness and the adhesive strength or tack is improved, and the shear adhesive strength of the double-sided pressure-sensitive adhesive tape can be further increased. .
- a crosslinking structure is formed between the main chains of the resin (the acrylic copolymer and / or the tackifying resin) constituting the acrylic pressure-sensitive adhesive layer by adding a crosslinking agent.
- a crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Of these, isocyanate-based crosslinking agents are preferred.
- the isocyanate group of the isocyanate-based cross-linking agent reacts with the alcoholic hydroxyl group in the resin constituting the acrylic pressure-sensitive adhesive layer, and the acrylic pressure-sensitive adhesive layer.
- the cross-linking becomes loose. Accordingly, the acrylic pressure-sensitive adhesive layer can disperse the intermittently applied peeling stress, and the shear adhesive strength of the double-sided pressure-sensitive adhesive tape is further improved.
- the addition amount of the crosslinking agent is preferably 0.01 to 10 parts by weight and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the acrylic copolymer.
- the degree of cross-linking of the acrylic pressure-sensitive adhesive layer is preferably 5 to 40% by weight, because it may be easily peeled off from the adherend when a load in a large shear direction is applied, whether it is too high or too low. More preferred is 40% by weight, and particularly preferred is 15 to 35% by weight.
- the double-sided pressure-sensitive adhesive tape of the present invention has a total thickness of 80 to 150 ⁇ m.
- the double-sided pressure-sensitive adhesive tape of the present invention can achieve both shock absorption and removability even when it is thin, despite having a base material made of a foam.
- the minimum with the preferable total thickness of a double-sided adhesive tape is 90 micrometers, and a preferable upper limit is 100 micrometers.
- the double-sided pressure-sensitive adhesive tape of the present invention preferably has a tensile strength in the MD direction of 12 N / 10 mm or more and a tensile strength in the TD direction of 8 N / 10 mm or more.
- the double-sided pressure-sensitive adhesive tape of the present invention has a tensile strength in the MD direction and TD direction that is equal to or higher than the above lower limit, the double-sided pressure-sensitive adhesive tape does not extend excessively when peeled off, thereby improving the removability of the double-sided pressure-sensitive adhesive tape Can do.
- a more preferable lower limit of the tensile strength in the MD direction is 13 N / 10 mm, and a preferable lower limit of the tensile strength in the TD direction is 9 N / 10 mm.
- the upper limit of the tensile strength in the MD direction is not particularly limited, but a preferable upper limit is 25 N / 10 mm, and a more preferable upper limit is 20 N / 10 mm.
- the upper limit of the tensile strength in the TD direction is not particularly limited, but the preferable upper limit is 15 N / 10 mm, and the more preferable upper limit is 12 N / 10 mm.
- the elongation at this time is not particularly limited, but is preferably about 200 to 500%.
- tensile strength can be measured by the method based on JISZ0237.
- the tensile strength can be achieved by adjusting the average cell diameter of the base material and the degree of crosslinking and shear modulus of the acrylic pressure-sensitive adhesive layer.
- a solution of an adhesive A is prepared by adding a solvent to an acrylic copolymer, a tackifier resin, and a cross-linking agent as necessary, and the solution of the adhesive A is applied to the surface of the substrate.
- the acrylic adhesive layer A is formed by completely removing and removing the solvent.
- a release film is overlaid on the formed acrylic pressure-sensitive adhesive layer A so that the release treatment surface faces the acrylic pressure-sensitive adhesive layer A.
- a release film different from the above release film is prepared, the adhesive B solution is applied to the release treatment surface of the release film, and the solvent in the solution is completely removed by drying, thereby releasing the release film.
- a laminated film in which the acrylic pressure-sensitive adhesive layer B is formed on the surface of the mold film is produced.
- the obtained laminated film is superposed on the back surface of the base material on which the acrylic pressure-sensitive adhesive layer A is formed, with the acrylic pressure-sensitive adhesive layer B facing the back surface of the base material to produce a laminate.
- a double-sided pressure-sensitive adhesive tape having an acrylic pressure-sensitive adhesive layer on both surfaces of the base material and having the surface of the acrylic pressure-sensitive adhesive layer covered with a release film can be obtained. it can.
- two sets of laminated films are produced in the same manner, and a laminated body is produced by superposing these laminated films on both sides of the base material with the acrylic adhesive layer of the laminated film facing the base material. Then, by pressing this laminate with a rubber roller or the like, a double-sided pressure-sensitive adhesive tape having an acrylic pressure-sensitive adhesive layer on both surfaces of the base material and the surface of the acrylic pressure-sensitive adhesive layer covered with a release film can be obtained. Good.
- the use of the double-sided pressure-sensitive adhesive tape of the present invention is not particularly limited, it is used for bonding and fixing parts constituting portable electronic devices such as battery packs to the device main body, and used for bonding and fixing automobile members to the vehicle main body. (That is, used for fixing electronic device parts or for mounting on-vehicle parts) and the like are preferable.
- the double-sided pressure-sensitive adhesive tape of the present invention can be used for adhesive fixing of components in large-sized portable electronic devices, adhesive fixing of automobile members (for example, in-vehicle panels), and the like.
- the shape of the double-sided pressure-sensitive adhesive tape of the present invention in these applications is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape.
- the double-sided adhesive tape excellent in impact absorption and removability can be provided.
- the long sheet-like polyolefin resin composition was crosslinked by irradiating 4.5 Mrad of an electron beam with an acceleration voltage of 500 kV on both sides thereof.
- the cross-linked polyolefin resin composition was cut into 400 ⁇ 400 mm and pressed with a press machine until the thickness became about 150 ⁇ m.
- the polyolefin resin composition after pressurization is continuously sent into a foaming furnace maintained at 250 ° C. with hot air and an infrared heater to be heated and foamed, and the draw ratio of MD is 1.3 times while foaming.
- a base material (A) having a thickness of 60 ⁇ m was obtained by stretching the stretching ratio of TD at 2.0 times. The average cell diameter, density, and expansion ratio of the obtained substrate were measured.
- a reactor equipped with a thermometer, stirrer, and condenser is 75 parts by weight of butyl acrylate, 21 parts by weight of 2-ethylhexyl acrylate, 3.8 parts by weight of acrylic acid, 0.2 part by weight of 2-hydroxyethyl acrylate, and acetic acid
- the reactor was heated to start refluxing.
- 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator in the reactor.
- the solution was refluxed at 70 ° C. for 5 hours to obtain a solution of the acrylic copolymer (a).
- the acrylic copolymer (b) having a weight average molecular weight of 1.4 million was the same as the acrylic copolymer (a) except that 62 parts by weight of butyl acrylate, 24 parts by weight of 2-ethylhexyl acrylate, and 10 parts by weight of ethyl acrylate were used. A solution was obtained.
- a pressure-sensitive adhesive (B) was obtained in the same manner as the pressure-sensitive adhesive (A) except that the solution of the obtained acrylic copolymer (b) was used.
- Example 1 A release paper having a thickness of 150 ⁇ m was prepared, the acrylic pressure-sensitive adhesive A was applied to the release-treated surface of the release paper, and dried at 100 ° C. for 5 minutes, thereby forming an acrylic pressure-sensitive adhesive layer having a thickness of 20 ⁇ m.
- This acrylic pressure-sensitive adhesive layer was bonded to the surface of the polyolefin foam shown in Table 1.
- the same acrylic pressure-sensitive adhesive layer as above was bonded to the opposite surface of the polyolefin foam. This obtained the double-sided adhesive tape with the total thickness of 100 micrometers covered with the release paper.
- Examples 2 to 6, Comparative Examples 1 to 5 A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the type of base material, the type of acrylic pressure-sensitive adhesive, and the thickness of one side of the acrylic pressure-sensitive adhesive layer were changed to those shown in the table.
- the obtained double-sided adhesive tape was cut into a size of 10 mm ⁇ 200 mm to prepare a measurement sample. Subsequently, based on JISZ0237, the tensile test was done at the speed of 5 mm / sec, and tensile strength (N / 10mm) and elongation rate (%) were computed.
- FIG. 1 the schematic diagram which shows the measuring method of the removability of a double-sided adhesive tape is shown.
- the double-sided adhesive tape was cut into 10 mm ⁇ 60 mm.
- the cut double-sided pressure-sensitive adhesive tape was attached to a polycarbonate (PC) plate having a thickness of 2 mm.
- PC polycarbonate
- the same PC plate as the one with the double-sided adhesive tape attached is attached so that the end of the PC plate is 1 cm from the end of the test piece, and after crimping at 5 kg for 10 seconds
- the test piece was obtained by allowing to stand at 23 ° C. for 24 hours. Peel off the double-sided adhesive tape on the test piece after standing, and peel it off as “ ⁇ ” when it is peeled off without tearing along the way, and “ ⁇ ” when the double-sided adhesive tape is broken during peeling Sex was evaluated.
- FIG. 2 shows a schematic diagram of a test device used for a drop impact test of double-sided pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples.
- the obtained double-sided adhesive tape was punched into an outer diameter of 46 mm, a length of 61 mm, an inner diameter of 44 mm, and a length of 59 mm to produce a frame-shaped test piece having a width of 1 mm.
- the test piece 3 from which the release paper was peeled off from the polycarbonate plate 5 having a thickness of 38 mm and a square hole having a width of 38 mm and a length of 50 mm in the center portion was arranged so that the square hole was located in the center.
- FIG. 3 shows a schematic diagram of a test method for a drop impact test of double-sided pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples. As shown in FIG.
- the produced test apparatus was turned over and fixed to the support base, and a 150 g iron weight 6 having a size passing through the square hole was dropped so as to pass through the square hole.
- the height at which the iron weight 6 is dropped is gradually increased, and the height at which the iron weight 6 is dropped when the test piece 3 and the glass plate 4 are peeled off due to the impact applied by the dropping of the iron weight 6.
- the measurement was made and the drop impact resistance was evaluated with “ ⁇ ” when the height of the iron weight 6 dropped was 30 cm or more and “X” when the height was less than 30 cm.
- the double-sided adhesive tape excellent in impact absorption and removability can be provided.
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- Chemical & Material Sciences (AREA)
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- Adhesive Tapes (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
特許文献1及び2には、基材層の少なくとも片面にアクリル系粘着剤層が積層一体化されており、基材層が、特定の架橋度及び気泡のアスペクト比を有する架橋ポリオレフィン系樹脂発泡シートである衝撃吸収テープが記載されている。
以下、本発明を詳述する。
上記ポリオレフィン発泡体は、後述するMD方向及びTD方向の平均気泡径を満たすポリオレフィン発泡体ならば特に限定されず、例えば、ポリエチレン系発泡体、ポリプロピレン系発泡体、エチレン-プロピレン系発泡体等が挙げられる。中でも、ポリエチレン系発泡体であることが好ましい
上記ポリオレフィン発泡体が、30μm以上、70μm以下という小さな平均気泡径を有することによって、基材を薄くした場合であっても強度を保つことができ、衝撃吸収性と再剥離性を両立しながらも薄型の両面粘着テープとすることができる。上記ポリオレフィン発泡体の平均気泡径の好ましい下限は、35μm、より好ましい下限は40μmである。また、上記平均気泡径の好ましい上限は65μm、より好ましい上限は55μmである
上記平均気泡径を小さくする方法としては、発泡前に樹脂を加圧する方法等が挙げられる。発泡前に樹脂を加圧することで、発泡時に気泡の成長を抑えることができる。また、発泡時のMD方向及びTD方向への延伸率が小さいほど、MD方向及びTD方向の気泡径を小さくすることができるため、発泡前に加圧して樹脂の厚みを薄くすることで、発泡時の延伸を抑えながらも薄い基材とし、かつ、気泡を小さくすることができる。
なお、MD方向(Machine Direction)とは、ポリオレフィン発泡体をシート状に押出加工する際の押出方向をいい、TD方向(Transverse Direction)とはMD方向に対して垂直方向をいう。
まず、ポリオレフィン発泡体のサンプルを50mm四方にカットし、液体窒素に1分間浸した後、カミソリ刃でMD方向及び厚さ方向に平行な面に沿って切断する。次いで、デジタルマイクロスコープ(例えば、キーエンス社製、「VHX-900」等)を用いて、200倍倍率で拡大写真を撮影し、MD方向における長さ2mmの切断面に存在する全ての気泡についてMD方向の気泡径を測定する。その操作を5回繰り返し、全てのMD方向の気泡径の平均値をMD方向の平均気泡径とする。
上記TD方向の平均気泡径も、ポリオレフィン発泡体のサンプルをTD方向及び厚さ方向に平行な面に沿って切断する以外は、同様にして測定することができる。
即ち、まず、ポリオレフィン発泡体のサンプルにおいて、厚さ方向に垂直な任意の一方向を選択して第一方向とし、第一方向及び厚さ方向に垂直な方向を第二方向とする。次いで、ポリオレフィン発泡体のサンプルを上記第一方向及び厚さ方向に平行な面に沿って切断し、上記の測定方法と同様にして上記第一方向の平均気泡径を測定する。得られた平均気泡径をMD方向の平均気泡径として扱う。更に、ポリオレフィン発泡体のサンプルを上記第二方向及び厚さ方向に平行な面に沿って切断する以外は、上記の測定方法と同様にして測定し、得られた平均気泡径をTD方向の平均気泡径として扱う。
なお、発泡倍率は、JISK-6767に準拠して電子比重計(例えば、ミラージュ社製、「ED120T」)を使用して測定した密度の逆数として算出できる。
(1)ポリオレフィン系樹脂、熱分解型発泡剤、及びその他の添加剤を押出機に供給して溶融混練し、押出機からシート状に押出すことによってシート状にされたポリオレフィン系樹脂組成物を得る工程。
(2)シート状にされたポリオレフィン系樹脂組成物を架橋する工程。
(3)架橋させたシート状のポリオレフィン系樹脂組成物を加圧し、その後加熱して、熱分解型発泡剤を発泡させ、MD方向又はTD方向の何れか一方又は双方に延伸する工程。
なお、ポリオレフィン発泡体の製造方法としては、この方法のほかに、国際公開第2005/007731号に記載された方法により製造することもできる。
上記ポリエチレン系樹脂は、エチレン単独重合体であってもよいが、エチレンと、少量のα-オレフィンとを共重合することにより得られるエチレン-α-オレフィン共重合体であることが好ましい。上記ポリエチレン系樹脂をエチレンと少量のα-オレフィンとの共重合体とすることで、発泡体の柔軟性を高めて衝撃吸収性をより高めることができる。上記エチレン-α-オレフィン共重合体の中でも、直鎖状低密度ポリエチレンがより好ましい。
上記エチレン-α-オレフィン共重合体におけるα-オレフィンの好ましい上限は30重量%、より好ましい上限は10重量%である。
なお、密度はASTM D792に準拠して測定された値である。
上記プロピレン-α-オレフィン共重合体におけるα-オレフィンとしては、例えば、エチレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン等が挙げられる。中でも、炭素数6~12のα-オレフィンであることが好ましい。
このようなメタロセン化合物は、活性点の性質が均一であり各活性点が同じ活性度を備えている。その結果、上記メタロセン化合物を用いて合成した重合体は、分子量、分子量分布、組成、組成分布等の均一性が高くなるため、上記メタロセン化合物を用いて合成した重合体を含むシートを架橋した場合には、架橋が均一に進行する。均一に架橋されたシートは、均一に延伸しやすくなるため、ポリオレフィン発泡体の厚さを均一にしやすくなる。
また、上記環式化合物をオリゴマーとして重合したものをリガンドとして用いてもよい。
更に、π電子系の不飽和化合物以外にも、塩素や臭素等の一価のアニオンリガンド、二価のアニオンキレートリガンド、炭化水素、アルコキシド、アリールアミド、アリールオキシド、アミド、アリールアミド、ホスフィド、アリールホスフィド等を用いてもよい。
上記任意成分としては、ポリオレフィン系樹脂以外の樹脂、ゴムが挙げられる。これらの任意成分は、合計でポリオレフィン系樹脂よりも少ない含有量であることが好ましく、具体的には、ポリオレフィン系樹脂100重量部に対して50重量部以下が好ましく、30重量部以下であることがより好ましい。
上記分解温度調整剤は、熱分解型発泡剤の分解温度を低くしたり、分解速度を速めたりすることで、発泡体の表面状態等を調整するものである。
分解温度調整剤としては、例えば、酸化亜鉛、ステアリン酸亜鉛、尿素等が挙げられる。
上記ポリオレフィン系樹脂100重量部に対する上記分解温度調整剤の含有量は、0.01~5重量部が好ましい。
上記架橋助剤としては、例えば、多官能モノマー等が挙げられる。具体的には、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、トリメリット酸トリアリルエステル、1,2,4-ベンゼントリカルボン酸トリアリルエステル、トリアリルイソシアヌレート等の1分子中に3個の官能基を持つ化合物や、1,6-ヘキサンジオールジメタクリレート、1,9-ノナンジオールジメタクリレート、1,10-デカンジオールジメタクリレート、ジビニルベンゼン等の1分子中に2個の官能基を持つ化合物、フタル酸ジアリル、テレフタル酸ジアリル、イソフタル酸ジアリル、エチルビニルベンゼン、ネオペンチルグリコールジメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート等が挙げられる。
これらの架橋助剤は、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
なお、ポリオレフィン系樹脂組成物のゲル分率(架橋度)は、以下のようにして測定することができる。
即ち、ポリオレフィン発泡体から約50mgの試験片を採取し、試験片の重量A(mg)を精秤する。次に、この試験片を105℃のキシレン30cm3中に浸漬して24時間放置した後、200メッシュの金網で濾過して金網上の不溶解分を採取、真空乾燥し、不溶解分の重量B(mg)を精秤する。得られた値から、下記式によりゲル分率(重量%)を算出する。
ゲル分率(重量%)=(B/A)×100
上記有機過酸化物の添加量は、ポリオレフィン系樹脂100重量部に対し、0.01~5重量部が好ましく、0.1~3重量部がより好ましい。上記有機過酸化物の添加量が上記範囲内であることで、ポリオレフィン系樹脂組成物の架橋が進行しやすく、また、得られるポリオレフィン発泡体中に存在する有機過酸化物の分解残渣の量を抑制することができる。
なお、ポリオレフィン系樹脂組成物の発泡は、熱分解型発泡剤を用いる例に限定されず、ブタンガス等による物理発泡を用いてもよい。
上記アクリル粘着剤層の厚みは、片面のアクリル粘着剤層の厚みが50μm以下であることが好ましい。上記アクリル粘着剤層の厚みが50μm以下であることで、両面粘着テープの耐衝撃性及びせん断粘着力と両面粘着テープの薄さを両立することができる。上記アクリル粘着剤層のより好ましい上限は30μmである。上記アクリル粘着剤層の厚みの下限は特に制限されないが、8μmが好ましく、10μmがより好ましい。
全モノマー混合物に占めるブチルアクリレートの好ましい含有量は、40~80重量%である。ブチルアクリレートの含有量が40重量%以上であることで、上記アクリル粘着剤層が適度な柔らかさと凝集力になり、両面粘着テープのせん断粘着力を向上させることができる。ブチルアクリレートの含有量が80重量%以下であることで、上記アクリル粘着剤層が適度な硬さとなり、粘着力又はタックが上がって両面粘着テープのせん断粘着力を向上させることができる。
全モノマー混合物に占める2-エチルヘキシルアクリレートの好ましい含有量は、10~40重量%である。2-エチルヘキシルアクリレートの含有量が10重量%以上であることで、上記アクリル粘着剤層の粘着力が上がり、両面粘着テープのせん断粘着力を向上させることができる。2-エチルヘキシルアクリレートの含有量が40重量%以下であることで、上記アクリル粘着剤層が適度な柔らかさと凝集力になり、両面粘着テープのせん断粘着力を向上させることができる。
上記共重合可能な他の重合性モノマーとして、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル等のアルキル基の炭素数が1~3の(メタ)アクリル酸アルキルエステル、メタクリル酸トリデシル、(メタ)アクリル酸ステアリル等のアルキル基の炭素数が13~18の(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸ヒドロキシアルキル、グリセリンジメタクリレート、(メタ)アクリル酸グリシジル、2-メタクリロイルオキシエチルイソシアネート、(メタ)アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸、フマル酸等の官能性モノマーが挙げられる。
上記重合開始剤は特に限定されず、例えば、有機過酸化物、アゾ化合物等が挙げられる。上記有機過酸化物として、例えば、1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、2,5-ジメチル-2,5-ビス(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート等が挙げられる。上記アゾ化合物として、例えば、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル等が挙げられる。これらの重合開始剤は単独で用いてもよいし、2種以上を併用してもよい。
重量平均分子量を上記範囲に調整するためには、重合開始剤、重合温度等の重合条件を調整すればよい。
なお、重量平均分子量(Mw)とは、GPC(Gel Permeation Chromatography:ゲルパーミエーションクロマトグラフィ)による標準ポリスチレン換算の重量平均分子量である。
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、C5系石油樹脂、C9系石油樹脂、C5-C9共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、2種以上を併用してもよい。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤が好ましい。上記アクリル粘着剤層にイソシアネート系架橋剤が添加されることで、イソシアネート系架橋剤のイソシアネート基と上記アクリル粘着剤層を構成する樹脂中のアルコール性水酸基とが反応して、上記アクリル粘着剤層の架橋が緩くなる。従って、上記アクリル粘着剤層は、断続的に加わる剥離応力を分散させることができ、両面粘着テープのせん断粘着力がより向上する。
上記架橋剤の添加量は、上記アクリル共重合体100重量部に対して0.01~10重量部が好ましく、0.1~3重量部がより好ましい。
なお、アクリル粘着剤層の架橋度は、アクリル粘着剤層をW1(g)採取し、このアクリル粘着剤層を酢酸エチル中に23℃にて24時間浸漬して不溶解分を200メッシュの金網で濾過し、金網上の残渣を真空乾燥して乾燥残渣の重量W2(g)を測定し、下記式(1)により算出する。
架橋度(重量%)=100×W2/W1 (1)
本発明の両面粘着テープのMD方向及びTD方向の引っ張り強さが上記下限以上であると、両面粘着テープを剥がす際に過度に伸びることがないため、両面粘着テープの再剥離性を向上させることができる。上記MD方向の引っ張り強さのより好ましい下限は13N/10mm、上記TD方向の引っ張り強さの好ましい下限は9N/10mmである。
上記MD方向の引っ張り強さの上限は特に制限されないが、好ましい上限は25N/10mm、より好ましい上限は20N/10mmである。上記TD方向の引っ張り強さの上限は特に制限されないが、好ましい上限は15N/10mm、より好ましい上限は12N/10mmである。
なお、このときの伸び率は特に限定されないが、200~500%程度となることが好ましい。
なお、引っ張り強さは、JISZ0237に準拠した方法で測定することができる。
上記引っ張り強さは、上記基材の平均気泡径並びに上記アクリル粘着剤層の架橋度及びせん断弾性率を調節することで達成することができる。
まず、アクリル共重合体、粘着付与樹脂、必要に応じて架橋剤等に溶剤を加えて粘着剤Aの溶液を作製して、この粘着剤Aの溶液を基材の表面に塗布し、溶液中の溶剤を完全に乾燥除去してアクリル粘着剤層Aを形成する。次に、形成されたアクリル粘着剤層Aの上に離型フィルムをその離型処理面がアクリル粘着剤層Aに対向した状態に重ね合わせる。
次いで、上記離型フィルムとは別の離型フィルムを用意し、この離型フィルムの離型処理面に粘着剤Bの溶液を塗布し、溶液中の溶剤を完全に乾燥除去することにより、離型フィルムの表面にアクリル粘着剤層Bが形成された積層フィルムを作製する。得られた積層フィルムをアクリル粘着剤層Aが形成された基材の裏面に、アクリル粘着剤層Bが基材の裏面に対向した状態に重ね合わせて積層体を作製する。そして、上記積層体をゴムローラ等によって加圧することによって、基材の両面にアクリル粘着剤層を有し、かつ、アクリル粘着剤層の表面が離型フィルムで覆われた両面粘着テープを得ることができる。
これらの用途における本発明の両面粘着テープの形状は特に限定されないが、長方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。
ポリオレフィン系樹脂としての直鎖状低密度ポリエチレン(エクソンケミカル社製、商品名「Exact3027」、密度:0.900g/cm3)100重量部、熱分解型発泡剤としてのアゾジカルボンアミド3.5重量部、分解温度調整剤としての酸化亜鉛1.0重量部、及び酸化防止剤としての2,6-ジ-t-ブチル-p-クレゾール0.5重量部を押出機に供給して130℃で溶融混練し、厚さ約200μmの長尺シート状のポリオレフィン系樹脂組成物を押出した。
次に、上記長尺シート状のポリオレフィン系樹脂組成物を、その両面に加速電圧500kVの電子線を4.5Mrad照射して架橋した。次いで、架橋したポリオレフィン系樹脂組成物を400×400mmにカットし、プレス機で厚さが約150μmになるまで加圧した。加圧後のポリオレフィン系樹脂組成物を熱風及び赤外線ヒーターにより250℃に保持された発泡炉内に連続的に送り込んで加熱して発泡させると共に、発泡させながらMDの延伸倍率を1.3倍、TDの延伸倍率を2.0倍として延伸させることにより、厚さ60μmの基材(A)を得た。得られた基材について平均気泡径、密度、発泡倍率を測定した。
ポリオレフィン系樹脂組成物の配合をアゾジカルボンアミド1.5~5.0重量部に変更すると共に、TDの延伸倍率を1.5倍~2.0倍に調整した点を除いて基材(A)の製造と同様にして、基材(B)~(D)及び(G)を得た。得られた基材について平均気泡径、密度、発泡倍率を測定した。
ポリオレフィン系樹脂組成物の配合をアゾジカルボンアミド2.0~3.5重量部に変更すると共に、プレス機で加圧することなく、熱風及び赤外線ヒーターにより250℃に保持された発泡炉内に連続的に送り込んで加熱して発泡させた点、TDの延伸倍率を2.5倍~3.5倍に調整した点を除いて基材(A)の製造と同様にして、基材(E)~(F)を得た。得られた基材について平均気泡径、密度、発泡倍率を測定した。
温度計、撹拌機、冷却管を備えた反応器にブチルアクリレート75重量部、2-エチルヘキシルアクリレート21重量部、アクリル酸3.8重量部、2-ヒドロキシエチルアクリレート0.2重量部、及び、酢酸エチル80重量部を加え、窒素置換した後、反応器を加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル0.1重量部を添加した。70℃、5時間還流させて、アクリル共重合体(a)の溶液を得た。得られたアクリル共重合体(a)について、カラムとしてWater社製「2690 Separations Model」を用いてGPC法により重量平均分子量を測定したところ、70万であった。
得られたアクリル共重合体(a)の溶液に含まれるアクリル共重合体(a)の固形分100重量部に対して、重合ロジンエステル15重量部、テルペンフェノール15重量部、水添ロジンエステル10重量部、酢酸エチル(不二化学薬品社製)125重量部、イソシアネート系架橋剤(日本ポリウレタン社製 商品名「コロネートL45」)2.2重量部を添加し、撹拌して、粘着剤(A)を得た。
ブチルアクリレート62重量部、2-エチルヘキシルアクリレート24重量部、エチルアクリレート10重量部としたこと以外はアクリル共重合体(a)と同様にして、重量平均分子量140万のアクリル共重合体(b)の溶液を得た。
得られたアクリル共重合体(b)の溶液を用いたこと以外は粘着剤(A)と同様にして、粘着剤(B)を得た。
厚み150μmの離型紙を用意し、この離型紙の離型処理面にアクリル粘着剤Aを塗布し、100℃で5分間乾燥させることにより、厚み20μmのアクリル粘着剤層を形成した。このアクリル粘着剤層を、表1に示すポリオレフィン発泡体の表面と貼り合わせた。次いで、同様の要領で、このポリオレフィン発泡体の反対の表面にも上記と同じアクリル粘着剤層を貼り合わせた。これにより、離型紙で覆われた総厚み100μmの両面粘着テープを得た。
基材の種類と、アクリル粘着剤の種類、アクリル粘着剤層の片面厚みを表に記載のものに変更したこと以外は実施例1と同様にして、両面粘着テープを得た。
得られた両面粘着テープを10mm×200mmの大きさに切り取り測定用サンプルを作製した。次いで、JISZ0237に準拠して、5mm/secの速度で引っ張り試験を行い、引っ張り強さ(N/10mm)と伸び率(%)を算出した。
実施例、比較例で得られた両面粘着テープについて以下の評価を行った。結果を表1及び表2に示した。
図1に、両面粘着テープの再剥離性の測定方法を示す模式図を示す。
まず、両面粘着テープを10mm×60mmに切断した。次いで、厚み2mmのポリカーボネート(PC)板に切断した両面粘着テープを貼り付けた。その後、図1に示すように、両面粘着テープを貼り付けたものと同様のPC板を、PC板の端が試験片の端から1cmの位置になるように貼り合わせ、5kgで10秒間圧着後、23℃で24時間静置して試験片を得た。静置後の試験片の両面粘着テープを引っ張りながら剥がし、途中で千切れずに剥がせた場合を「○」、剥がしている途中で両面粘着テープが千切れた場合を「×」として再剥離性を評価した。
(1)試験装置の作製
図2に、実施例、比較例で得られた両面粘着テープの落下衝撃試験に用いた試験装置の模式図を示す。
得られた両面粘着テープを外径が幅46mm、長さ61mm、内径が幅44mm、長さ59mmに打ち抜き、幅1mmの枠状の試験片を作製した。次いで、図2に示すように、中央部分に幅38mm、長さ50mmの四角い穴のあいた厚さ2mmのポリカーボネート板5に対して離型紙を剥がした試験片3を四角い穴が中央に位置するように貼り付けた後、試験片3の上面から幅50mm、長さ74mm、厚さ4mmのガラス板4を試験片3が中央に位置するように貼り付け、上面に位置するガラス板4側から5kgfの力を10秒間加えて上下に位置するガラス板4及びポリカーボネート板5と試験片とを圧着し、23℃で24時間放置して試験装置を作製した。
(2)耐衝撃性の評価
図3に、実施例、比較例で得られた両面粘着テープの落下衝撃試験の試験方法の模式図を示す。図3に示すように、作製した試験装置を裏返して支持台に固定し、四角い穴を通過する大きさの150gの鉄製の重り6を四角い穴を通過するように落とした。鉄製の重り6を落とす高さを徐々に高くしていき、鉄製の重り6の落下により加わった衝撃により試験片3とガラス板4とが剥がれた時の鉄製の重り6を落とした高さを計測し、鉄製の重り6を落とした高さが30cm以上であった場合を「○」、30cm未満であった場合を「×」として耐落下衝撃性を評価した。
2 両面粘着テープ
3 試験片
4 ガラス板
5 ポリカーボネート板
6 鉄製の重り
Claims (6)
- ポリオレフィン発泡体からなる基材の両面にアクリル粘着剤層を有する両面粘着テープであって、
前記ポリオレフィン発泡体からなる基材の厚みが50~120μmであり、
前記ポリオレフィン発泡体からなる基材のMD方向及びTD方向における平均気泡径が30μm以上、70μm以下であり、
両面粘着テープの総厚みが80~150μmである
ことを特徴とする両面粘着テープ。 - ポリオレフィン発泡体の発泡倍率が1.4~2cm3/gであることを特徴とする請求項1記載の両面粘着テープ。
- アクリル粘着剤層の厚みが片面で50μm以下であることを特徴とする請求項1又は2記載の両面粘着テープ。
- MD方向の引っ張り強さが12N/10mm以上かつTD方向の引っ張り強さが8N/10mm以上であることを特徴とする請求項1、2又は3記載の両面粘着テープ。
- 前記ポリオレフィン発泡体がポリエチレン系発泡体であることを特徴とする請求項1、2、3又は4記載の両面粘着テープ。
- 電子機器部品固定用途または車載部品固定用途に用いられることを特徴とする請求項1、2、3、4又は5記載の両面粘着テープ。
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| WO2019219519A1 (en) * | 2018-05-15 | 2019-11-21 | Tesa Se | Sebum-proof foam tape for an electronic device |
| WO2020175368A1 (ja) * | 2019-02-25 | 2020-09-03 | 積水化学工業株式会社 | 両面粘着テープ、電子機器部品及び電子機器 |
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| JP6966650B2 (ja) * | 2019-04-24 | 2021-11-17 | 積水化学工業株式会社 | 粘着テープ |
| KR102172041B1 (ko) * | 2019-06-13 | 2020-11-02 | 주식회사 신양 | 재박리형 점착제 및 점착제 재료의 제조방법 |
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| JP2019065191A (ja) * | 2017-09-29 | 2019-04-25 | 積水化学工業株式会社 | 樹脂発泡シート、樹脂発泡シートの製造方法、及び粘着テープ |
| JP7063566B2 (ja) | 2017-09-29 | 2022-05-09 | 積水化学工業株式会社 | 樹脂発泡シート、樹脂発泡シートの製造方法、及び粘着テープ |
| WO2019219519A1 (en) * | 2018-05-15 | 2019-11-21 | Tesa Se | Sebum-proof foam tape for an electronic device |
| WO2020175368A1 (ja) * | 2019-02-25 | 2020-09-03 | 積水化学工業株式会社 | 両面粘着テープ、電子機器部品及び電子機器 |
| JPWO2020175368A1 (ja) * | 2019-02-25 | 2021-09-27 | 積水化学工業株式会社 | 両面粘着テープ、電子機器部品及び電子機器 |
| JP7044878B2 (ja) | 2019-02-25 | 2022-03-30 | 積水化学工業株式会社 | 両面粘着テープ、電子機器部品及び電子機器 |
Also Published As
| Publication number | Publication date |
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| CN107709492A (zh) | 2018-02-16 |
| KR20180101167A (ko) | 2018-09-12 |
| JPWO2017131082A1 (ja) | 2018-11-15 |
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