WO2023002982A1 - 粘着剤組成物、粘着剤層、及び粘着シート - Google Patents
粘着剤組成物、粘着剤層、及び粘着シート Download PDFInfo
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- WO2023002982A1 WO2023002982A1 PCT/JP2022/028058 JP2022028058W WO2023002982A1 WO 2023002982 A1 WO2023002982 A1 WO 2023002982A1 JP 2022028058 W JP2022028058 W JP 2022028058W WO 2023002982 A1 WO2023002982 A1 WO 2023002982A1
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- Prior art keywords
- sensitive adhesive
- pressure
- less
- dielectric loss
- ghz
- Prior art date
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- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
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- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- YHPUTXNFABTCGG-UHFFFAOYSA-N propyl 2-sulfanylacetate Chemical compound CCCOC(=O)CS YHPUTXNFABTCGG-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- YXIMCNGUIIEJMO-UHFFFAOYSA-N tert-butyl 2-sulfanylacetate Chemical compound CC(C)(C)OC(=O)CS YXIMCNGUIIEJMO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/40—Radiating elements coated with or embedded in protective material
-
- 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
Definitions
- the present invention relates to an adhesive composition, an adhesive layer, and an adhesive sheet. More particularly, the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet that are suitable for bonding components of a millimeter wave antenna.
- millimeter waves In order to enable ultra-high-speed, large-capacity communication, low latency, and multiple simultaneous connections in 5G, high-frequency electromagnetic waves with a frequency exceeding 24 GHz called millimeter waves are used, and the wavelength is shortened to the order of millimeters. This makes it possible to send a large amount of data at once.
- millimeter waves tend to be attenuated due to resonance absorption with rain, oxygen in the air, and water molecules, etc., and have strong straightness and are easy to reflect.
- Antennas used for millimeter wave communications (hereinafter sometimes referred to as "millimeter wave antennas") are required to have a higher antenna gain than conventional 4G communications.
- Patent Document 1 discloses a configuration in which a cover member is laminated on a base material provided with an antenna element as a millimeter wave antenna mounted on a portable communication device such as a smart phone. Adhesive is used for bonding.
- Patent Document 2 contains a polymer obtained by polymerizing a monomer mixture containing 2-ethylhexyl acrylate, a specific (meth)acrylic acid alkyl ester, and a hydroxyl group-containing monomer,
- a pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer having a dielectric constant of 3.5 or less at a frequency of 100 kHz is disclosed.
- Patent Document 3 a specific acrylic polymer, a vinyl monomer having a polyalkylene oxide chain, a photopolymerization initiator, and a cross-linking agent are contained, and the dielectric constant at a frequency of 1 MHz is 3.5 or less. Certain adhesive layers are disclosed.
- the materials that make up a millimeter wave antenna reduce millimeter waves due to the dielectric loss of the material.
- a characteristic of low dielectric loss is required.
- Low dielectric constant and low dielectric loss characteristics in high frequency bands are also required for adhesives used to bond members constituting millimeter wave antennas.
- water tends to absorb and block millimeter waves in the high frequency band as described above, the dielectric properties are required to be less susceptible to moisture.
- Patent Document 2 has a low dielectric constant at a low frequency (100 kHz), the dielectric loss in a high frequency band is not sufficiently low. Although it has a low dielectric constant, the dielectric loss in the high frequency band was not sufficiently low. In addition, it only describes the dielectric constant in the low frequency band and does not disclose information on the dielectric loss in the high frequency band, and it could not provide a solution to the problem to which the present application is directed.
- An object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer suitable for bonding members constituting a millimeter wave antenna.
- Another object of the present invention is to provide a pressure-sensitive adhesive layer which has a low dielectric constant and dielectric loss in a high frequency band, whose dielectric properties are not easily affected by moisture, and which is suitable for bonding members constituting a millimeter wave antenna. That's what it is.
- Another object of the present invention is to provide an adhesive having a pressure-sensitive adhesive layer that has a low dielectric constant and dielectric loss in a high frequency band, is less susceptible to moisture in terms of dielectric properties, and is suitable for bonding members constituting a millimeter wave antenna. It is to provide a sheet.
- the maximum value D fmin of the dielectric loss at a frequency of 28 GHz 65° C., 90% R.E.M. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H. The minimum value of dielectric loss at a frequency of 28 GHz while tracking the change in dielectric loss over time at
- the configuration in which the dielectric constant at a frequency of 28 GHz is 2.0 to 5.0 can improve the antenna gain of a millimeter wave antenna in which the constituent members are bonded using the pressure-sensitive adhesive composition. .
- the configuration that the dielectric loss at a frequency of 28 GHz is 0.0001 to 0.05 can improve the antenna gain of a millimeter wave antenna in which the constituent members are bonded using the pressure-sensitive adhesive composition. .
- the water vapor transmission rate (WVTR) at 430 g/m 2 /day or less is excellent in water resistance when applied as an adhesive layer to a millimeter wave antenna, etc., and reduces the radiation loss of millimeter waves. fluctuation can be suppressed.
- the change in dielectric loss at a frequency of 28 GHz is 0.006 or less, the change in dielectric loss due to moisture absorption is controlled to be low, and millimeter-wave radiation loss can be suppressed. . It is possible to obtain a pressure-sensitive adhesive composition that is excellent in water resistance and capable of suppressing millimeter-wave radiation loss when the amount of change in dielectric loss is 0.006 or less.
- the dielectric constant at a frequency of 60 GHz is preferably 2.0 to 5.0. This configuration is preferable in that the antenna gain of a millimeter wave antenna in which constituent members are bonded using the pressure-sensitive adhesive composition can be improved.
- the maximum value D fmin of the dielectric loss at a frequency of 60 GHz 65° C., 90% R.E.M. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H. The minimum value of dielectric loss at a frequency of 60 GHz while tracking the change in dielectric loss over time at
- the configuration in which the dielectric constant at a frequency of 60 GHz is 2 to 5 can improve the antenna gain of a millimeter wave antenna in which the constituent members are bonded together using the pressure-sensitive adhesive composition.
- the structure that the dielectric loss at a frequency of 60 GHz is 0.0001 to 0.05 can improve the antenna gain of a millimeter wave antenna in which the constituent members are bonded using the pressure-sensitive adhesive composition. .
- the water vapor permeability of 430 g/m 2 /day or less is excellent in water resistance when applied as an adhesive layer to a millimeter wave antenna, etc., and can suppress fluctuations in millimeter wave radiation loss. .
- the change in dielectric loss at a frequency of 60 GHz is 0.003 or less, the change in dielectric loss due to moisture absorption is controlled to be low, and millimeter-wave radiation loss can be suppressed. . It is possible to obtain a pressure-sensitive adhesive composition that has excellent water resistance and can suppress the radiation loss of millimeter waves when the amount of change in dielectric loss is 0.003 or less.
- the adhesive composition preferably has a total light transmittance of 85% or more as measured on an adhesive layer with a thickness of 25 ⁇ m.
- the adhesive composition preferably has a haze of 1.0% or less as measured on an adhesive layer with a thickness of 25 ⁇ m.
- the present invention also provides a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
- the present invention also provides an adhesive sheet having the adhesive layer.
- the present invention also provides a millimeter wave antenna comprising at least the adhesive sheet and a substrate, wherein the substrate has an antenna element on at least one side thereof, and the adhesive sheet is adhered to the surface of the substrate having the antenna element.
- the pressure-sensitive adhesive composition and pressure-sensitive adhesive layer of the present invention exhibit low dielectric constant and dielectric loss in the high frequency band of millimeter waves, and can suppress radiation loss of millimeter waves. Therefore, by using the pressure-sensitive adhesive sheet of the present invention to bond constituent members of a millimeter wave antenna together, a millimeter wave antenna exhibiting high antenna gain can be efficiently manufactured. Also, the pressure-sensitive adhesive composition of the present invention is less susceptible to moisture with respect to its dielectric properties. Therefore, a millimeter wave antenna using the pressure-sensitive adhesive sheet of the present invention is less susceptible to moisture, and can stably suppress the radiation loss of millimeter waves to a low level.
- FIG. 1 is a schematic diagram (sectional view) showing an embodiment of a millimeter wave antenna of the present invention.
- FIG. 2 is a schematic diagram (cross-sectional view) showing an embodiment of the millimeter wave antenna of the present invention.
- FIG. 3 is a schematic diagram (sectional view) showing an embodiment of the millimeter wave antenna of the present invention.
- FIG. 4 is a schematic diagram (cross-sectional view) showing an antenna laminate used in evaluation of transmission/reception characteristics.
- FIG. 4(a) is a side sectional view
- FIG. 4(b) is a top projection view.
- the adhesive composition of the first aspect of the present invention has a dielectric constant of 2.0 to 5.0 at a frequency of 28 GHz and a dielectric loss of 0.0001 to 0.05 at a frequency of 28 GHz.
- % R.I. H. is 430 g/m 2 /day or less, and the amount of change in dielectric loss calculated by the following formula is 0.006 or less.
- Change in dielectric loss D fmax - D fmin D fmax : 65° C., 90% R.I. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H.
- the maximum value D fmin of the dielectric loss at a frequency of 28 GHz 65° C., 90% R.E.M. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H. The minimum value of dielectric loss at a frequency of 28 GHz while tracking the change in dielectric loss over time at
- the adhesive composition of the second aspect of the present invention has a dielectric constant of 2.0 to 5.0 at a frequency of 60 GHz and a dielectric loss of 0.0001 to 0.05 at a frequency of 60 GHz. % R.I. H. is 430 g/m 2 /day or less, and the amount of change in dielectric loss calculated by the following formula is 0.003 or less.
- Change in dielectric loss D fmax - D fmin D fmax : 65° C., 90% R.I. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H. , the maximum value D fmin of the dielectric loss at a frequency of 60 GHz: 65° C., 90% R.E.M. H. After humidifying to saturation at 23°C ⁇ 1°C, 52 ⁇ 1% R.I. H. The minimum value of dielectric loss at a frequency of 60 GHz while tracking the change in dielectric loss over time at
- the pressure-sensitive adhesive composition of the present invention may have any form, for example, solvent type, emulsion type, hot melt type (hot melt type), non-solvent type (active energy ray curable type, e.g. monomer mixtures, or monomer mixtures and partial polymers thereof, etc.).
- the pressure-sensitive adhesive composition of the present invention may be solvent-based, that is, it may contain an organic solvent.
- the organic solvent may be any organic compound that is used as a solvent.
- hydrocarbon solvents such as cyclohexane, hexane, heptane, and methylcyclohexane
- aromatic solvents such as toluene and xylene
- butyl acetate, ethyl acetate, Ester solvents such as methyl acetate
- Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
- Alcohol solvents such as methanol, ethanol, propanol, butanol and isopropyl alcohol.
- the organic solvent may be a mixed solvent containing two or more organic solvents.
- the adhesive composition of the first aspect of the present invention has a controlled low dielectric constant at 28 GHz, and can suppress radiation loss of millimeter waves.
- the dielectric constant of the adhesive composition of the first aspect of the present invention at a frequency of 28 GHz is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.5 or less. .4 or less, and may be 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, or 2.9 or less.
- the lower limit is not particularly limited, it is preferably 2.0 or more, and may be 2.1 or more or 2.2 or more.
- the adhesive composition of the second aspect preferably has a dielectric constant within the above range at a frequency of 28 GHz.
- the permittivity is measured by the method described in the examples below.
- the "relative permittivity” is a value obtained by dividing the "dielectric constant" by the “vacuum permittivity”. "relative permittivity” shall be treated as synonymous.
- the pressure-sensitive adhesive composition of the first aspect of the present invention and the pressure-sensitive adhesive composition of the second aspect of the present invention may be collectively referred to as "the pressure-sensitive adhesive composition of the present invention".
- the pressure-sensitive adhesive composition of the first aspect of the present invention has controlled low dielectric loss at 28 GHz, and can suppress millimeter-wave radiation loss.
- the pressure-sensitive adhesive composition of the first aspect of the present invention has a dielectric loss of 0.050 or less, preferably 0.045 or less, more preferably 0.040 or less, still more preferably 0.035 or less, at a frequency of 28 GHz. It is preferably 0.030 or less, still more preferably 0.025 or less, and particularly preferably 0.020 or less.
- the lower limit is preferably 0.0001 or more, and may be 0.0005 or more or 0.0010 or more.
- the pressure-sensitive adhesive composition of the second aspect of the present invention preferably has a dielectric loss within the above range at a frequency of 28 GHz.
- the adhesive composition of the second aspect of the present invention has a controlled low dielectric constant at 60 GHz, and can suppress radiation loss of millimeter waves.
- the dielectric constant of the adhesive composition of the second aspect of the present invention at a frequency of 60 GHz is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, and still more preferably 3.5 or less. , 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, or 2.9 or less.
- the lower limit is not particularly limited, it is preferably 2.0 or more, and may be 2.1 or more or 2.2 or more.
- the pressure-sensitive adhesive composition of the first aspect of the present invention preferably has a dielectric constant within the above range at a frequency of 60 GHz.
- the pressure-sensitive adhesive composition of the second aspect of the present invention has controlled low dielectric loss at 60 GHz, and can suppress millimeter-wave radiation loss.
- the dielectric loss of the adhesive composition of the second aspect of the present invention at a frequency of 60 GHz is 0.050 or less, preferably 0.045 or less, more preferably 0.040 or less, still more preferably 0.035 or less, More preferably 0.030 or less, still more preferably 0.025 or less, particularly preferably 0.020 or less, 0.019 or less, 0.018 or less, 0.017 or less, 0.016 or less, 0.015 Below, it may be 0.014 or less, 0.013 or less, or 0.012 or less.
- the lower limit of dielectric loss at a frequency of 60 GHz is preferably 0.0001 or more, and may be 0.0005 or more or 0.0010 or more.
- the pressure-sensitive adhesive composition of the first aspect of the present invention preferably has a dielectric loss within the above range at a frequency of 60 GHz.
- the pressure-sensitive adhesive composition of the present invention is controlled to have a low water vapor transmission rate, it is possible to suppress the movement of water molecules in the pressure-sensitive adhesive composition, thereby suppressing variations in the radiation loss of millimeter waves. 40° C., 92% R.I. of the pressure-sensitive adhesive composition of the present invention. H.
- the lower limit of water vapor permeability is not particularly limited, but may be, for example, 10 g/m 2 /day or more, 20 g/m 2 /day or more, or 25 g/m 2 /day or more.
- the water vapor transmission rate (WVTR) is a value measured based on the cup method.
- the pressure-sensitive adhesive composition of the present invention controls the amount of change in dielectric loss due to moisture absorption to a low level, it is possible to suppress millimeter-wave radiation loss and its change over time.
- the amount of change in dielectric loss due to moisture absorption at a frequency of 28 GHz of the adhesive composition of the first aspect of the present invention is 0.006 or less, preferably 0.005 or less, more preferably 0.004 or less.
- the lower limit of the amount of change in dielectric loss due to moisture absorption at a frequency of 28 GHz is not particularly limited, but may be, for example, 0.0001 or more, 0.0002 or more, or 0.0003 or more.
- the radiation loss of millimeter waves can be stably suppressed in an environment of room temperature to high temperature in a state where the pressure-sensitive adhesive layer or the like is applied.
- the pressure-sensitive adhesive composition of the second aspect of the present invention has an amount of change in dielectric loss due to moisture absorption at a frequency of 28 GHz within the above range.
- the amount of change in dielectric loss due to moisture absorption at a frequency of 60 GHz of the adhesive composition of the second aspect of the present invention is 0.003 or less, preferably 0.002 or less, more preferably 0.001 or less.
- the lower limit of the amount of change is not particularly limited. It may be 0.0007 or more, 0.0008 or more, or 0.0009 or more.
- the pressure-sensitive adhesive composition of the first aspect of the present invention has an amount of change in dielectric loss due to moisture absorption at a frequency of 60 GHz within the above range.
- the pressure-sensitive adhesive composition of the present invention has a controlled low saturated moisture absorption rate, it is possible to suppress radiation loss of millimeter waves. 25° C., 90% R.I. of the pressure-sensitive adhesive composition of the present invention.
- H. is preferably 2.8% or less, more preferably 2.7% or less, still more preferably 2.6% or less, particularly preferably 2.5% or less, 2.4% or less, .3% or less, 2.2% or less, 2.1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5 % or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less , or 0.6% or less.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.3% or more, 0.4% or more, or 0.5% or more.
- H. is preferably 2.8% or less, more preferably 2.6% or less, still more preferably 2.4% or less, particularly preferably 2.3% or less, and 2.2% or less .1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% % or less, 1.2% or less, 1.1% or less, 1.0% or less, 0.9% or less, 0.8% or less, or 0.7% or less.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.4% or more, 0.5% or more, or 0.6% or more.
- 65°C, 90% R.I When the saturated moisture absorption rate of H is low, the radiation loss of millimeter waves can be suppressed even when the adhesive layer or the like is applied and placed in a high-temperature environment.
- H. is preferably 5.0% or less, more preferably 4.0% or less, still more preferably 3.5% or less, particularly preferably 3.0% or less, 2.8% or less, 2.6 % or less, 2.4% or less, 2.2% or less, 2.0% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1.0% or less , or 0.8% or less.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.4% or more, 0.5% or more, or 0.6% or more.
- the dielectric constant or dielectric loss at 28 GHz or 60 GHz of the adhesive composition of the present invention, the water vapor transmission rate, the saturated moisture absorption rate, and the amount of change in dielectric loss due to moisture absorption are adjusted by adjusting the monomer composition, the type and content of additives, etc. can be adjusted accordingly.
- the dielectric constant or dielectric loss at 28 GHz or 60 GHz, water vapor permeability, saturated moisture absorption, and the amount of change in dielectric loss due to moisture absorption are measured by the methods described in Examples below. .
- the dielectric constant, dielectric loss, water vapor permeability and saturated moisture absorption of the pressure-sensitive adhesive composition of the present invention are the dielectric constant, dielectric loss, water vapor permeability and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive composition of the present invention. It means the saturated moisture absorption rate.
- the base polymer that constitutes the pressure-sensitive adhesive composition of the present invention is not particularly limited. composition, synthetic rubber pressure-sensitive adhesive composition, etc.) contains as a base polymer, a silicone-based polymer contained as a base polymer in a silicone-based pressure-sensitive adhesive composition, and a polyester-based pressure-sensitive adhesive composition contains as a base polymer Polyester-based polymer, urethane-based polymer contained as a base polymer in a urethane-based pressure-sensitive adhesive composition, polyamide-based polymer contained as a base polymer in a polyamide-based pressure-sensitive adhesive composition, epoxy-based polymer contained in an epoxy-based pressure-sensitive adhesive composition as a base polymer Examples include polymers, vinyl alkyl ether polymers contained as base polymers in vinyl alkyl ether pressure-sensitive adhesive compositions, and fluoropolymers contained as base polymers in fluorine pressure-sensitive adhesive compositions. Among them, acrylic polymers and rubber polymers are preferred, and acrylic polymers are particularly preferred. In addition, the base poly
- Examples of the rubber-based polymer include natural rubber, styrene-butadiene rubber (SBR), polyisoprene (PIP), polyisobutylene (PIB), butene-based polymer (butene (1-butene, and cis- or trans-2-butene) and / or 2-methylpropene (isobutylene) as the main monomer), ABA type block copolymer rubber and its hydride, styrene-butadiene-styrene block copolymer rubber (SBS), styrene-isoprene- Styrene Block Copolymer Rubber (SIS), Styrene-Isobutylene-Styrene Block Copolymer Rubber (SIBS), Styrene-Vinyl Isoprene-Styrene Block Copolymer Rubber (SVIS), SBS Hydrogenated Styrene-Ethylene- Examples include butylene-styrene block
- the dielectric constant and dielectric loss in a high frequency band are controlled low, and the water resistance is improved. By doing so, deterioration of dielectric loss can be suppressed.
- the "mixture, partial polymer or copolymer" of the above methacrylate compound and (meth)acrylate compound may be referred to as a methacrylic copolymer.
- a "methacrylate compound” is a compound having a “methacryloyl group”
- a “(meth)acrylate compound” is a compound having at least one of an “acryloyl group” and a “methacryloyl group”.
- "(meth)acryl” represents either one or both of "acryl” and "methacryl”.
- the partially polymerized product means a composition in which one or more of the monomer components constituting the mixture is partially polymerized.
- base polymer refers to the main component (the component with the highest compounding ratio; the same shall apply hereinafter) among the polymer components contained in the pressure-sensitive adhesive composition. A component that accounts for more than % by weight.
- base polymer includes "a mixture of monomer components constituting the base polymer or a partially polymerized product of a mixture of monomer components constituting the base polymer".
- mixture of monomer components includes the case of being composed of a single monomer component and the case of being composed of two or more monomer components.
- the above-mentioned “partially polymerized mixture of monomer components” means a composition in which one or more of the constituent monomer components of the above-mentioned “mixture of monomer components” is partially polymerized. do.
- the content of the base polymer in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but is preferably 75% by weight or more (for example, 75 to 99.9% by weight), more preferably 85% by weight or more (for example, 85 to 99.9% by weight).
- the content of the methacrylic copolymer in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but is preferably 75% by mass or more (eg 75 to 99.9% by mass), more preferably 85% by mass or more (eg 85 to 99.9% by mass).
- the pressure-sensitive adhesive composition of the present invention is preferably a methacrylic pressure-sensitive adhesive composition having a mixture, a partial polymer thereof, or a copolymer thereof (methacrylic copolymer) as a base polymer.
- the content of the methacrylic copolymer is not particularly limited to 100% by mass of the total amount of the adhesive composition of the present invention, but is preferably 75% by mass or more (for example, 75 to 99.9% by mass). , preferably 85% by mass or more (for example, 85 to 99.9% by mass).
- the pressure-sensitive adhesive composition of the present invention includes, for example, a water-dispersible composition (emulsion type composition) containing the above copolymer as an essential component, and an active energy ray containing the above mixture or a partial polymer thereof as an essential component.
- a water-dispersible composition emulsion type composition
- an active energy ray containing the above mixture or a partial polymer thereof as an essential component.
- curable compositions among which compositions containing a mixture or a partially polymerized product thereof as an essential component are preferred.
- the methacrylic copolymer according to the present invention preferably contains a methacrylate compound having a hydrocarbon group with 6 or more carbon atoms and a (meth)acrylate compound having a crosslinkable functional group as constituent monomers.
- hydrocarbon group having 6 or more carbon atoms in the methacrylate compound preferably has an aliphatic group, an alicyclic-containing group, or an aromatic ring-containing group.
- hydrocarbon group-containing methacrylate compounds may be used alone or in combination of two or more.
- the main structural unit of the methacrylic copolymer is derived from a methacrylate compound and has an ⁇ -methyl group, the polarization near the main chain is reduced as compared with the case of the acrylate compound, and as a result, the dielectric loss is reduced. It is thought that In addition, since the methacryloyl group is more hydrophobic than the acryloyl group and suppresses moisture absorption, it is possible to suppress deterioration of dielectric loss in a high frequency band caused by moisture absorption and the amount of change in dielectric loss.
- the methacrylic copolymer can easily obtain an appropriate cohesive force and strong adhesiveness. Also, by increasing the gel fraction, it becomes easier to obtain excellent anti-foaming and peeling properties. Furthermore, it becomes easy to obtain appropriate flexibility in the pressure-sensitive adhesive layer, and it becomes easy to obtain excellent stress relaxation properties and excellent step followability.
- the number of carbon atoms in the hydrocarbon group is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more.
- the number of carbon atoms in the hydrocarbon group is preferably 22 or less, more preferably 20 or less, still more preferably 16 or less.
- methacrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an aliphatic group include hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, nonyl methacrylate, and methacrylic acid.
- lauryl methacrylate, tridecyl methacrylate, and isodecyl methacrylate are preferred.
- the content of the methacrylate compound in which the hydrocarbon group having 6 or more carbon atoms is an aliphatic group in the methacrylic copolymer according to the present invention is not particularly limited, but is 25% per 100% by mass of all structural units. % by mass or more, more preferably 25.0 to 99.5 mass %, still more preferably 30.0 to 99.3 mass %, still more preferably 40.0 to 99.0 mass %. It is preferable to use 25% by mass or more from the viewpoint of low dielectric constant and low dielectric loss in a high frequency band.
- the number of carbon atoms in the hydrocarbon group is preferably 6 or more, more preferably 8 or more.
- the number of carbon atoms in the hydrocarbon group is preferably 22 or less, more preferably 16 or less.
- methacrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an alicyclic group include methacrylic acid cycloalkyl esters having a cycloalkane ring (cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc.) , a methacrylic acid ester having a bicyclic hydrocarbon ring (pinane, pinene, bornane, norbornane, norbornene, etc.), and a tricyclic or higher aliphatic hydrocarbon ring (dicyclopentane ring, dicyclopentene ring, adamantane ring, tricyclic methacrylic acid esters having a cyclopentane ring, tricyclopentene ring, etc.).
- methacrylic acid cycloalkyl esters having a cycloalkane ring cyclopentane ring,
- methacrylic acid cycloalkyl esters examples include cyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, cycloheptyl methacrylate, and cyclooctyl methacrylate.
- methacrylic acid esters having a bicyclic hydrocarbon ring examples include bornyl methacrylate and isobornyl methacrylate.
- methacrylic acid ester having a hydrocarbon ring of three or more rings examples include dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, tricyclopentanyl methacrylate, 1-adamantyl methacrylate, and methacrylic acid 2. -methyl-2-adamantyl, 2-ethyl-2-adamantyl methacrylate and the like.
- the number of carbon atoms in the hydrocarbon group is preferably 6-14, more preferably 6-10.
- methacrylate compounds in which the hydrocarbon group having 6 or more carbon atoms is an aromatic ring-containing group include, for example, aromatic carbocyclic rings (e.g., monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.) Specific examples include benzyl methacrylate, phenyl methacrylate, naphthyl methacrylate, 6-(1,1′-biphenyl-4-yloxy)hexyl methacrylate, and the like.
- aromatic carbocyclic rings e.g., monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.
- Specific examples include benzyl methacrylate, phenyl methacrylate, naphthyl methacrylate, 6-(1,1′-biphenyl-4-yloxy)hexyl methacrylate
- the total content of the methacrylate compound in which the hydrocarbon group having 6 or more carbon atoms is an alicyclic-containing group or an aromatic ring-containing group in the methacrylic copolymer according to the present invention is not particularly limited, but all structural units It is preferably 1.0 to 60.0% by mass, more preferably 5.0 to 55.0% by mass, and still more preferably 10.0 to 50.0% by mass with respect to 100% by mass.
- the methacrylate compound may have a (poly)oxyalkylene chain.
- the hydrocarbon group having 6 or more carbon atoms is preferably at the end of the ester moiety in the methacrylate compound.
- the number of oxygen atoms in the (poly)oxyalkylene chain (that is, the number of repeating oxyalkylene groups) is preferably 1-10, more preferably 1-3.
- the hydrocarbon group having 6 or more carbon atoms at the terminal may be any of an aliphatic group, an alicyclic group, and an aromatic group, but is preferably an alicyclic group or an aromatic group, particularly Aromatic groups are preferred.
- methacrylate compounds having a (poly)oxyalkylene chain those having an aromatic group at the end thereof have a reduced polarizability in the entire repeating unit, which is effective in reducing dielectric loss in a high frequency band.
- the content of the methacrylate compound having the (poly)oxyalkylene chain in the methacrylic copolymer according to the present invention is not particularly limited, but is 1.0 to 30.0% by mass with respect to 100% by mass of all structural units. %, more preferably 5.0 to 25.0 mass %, still more preferably 10.0 to 20.0 mass %.
- the total content of the methacrylate compound having a hydrocarbon group having 6 or more carbon atoms in the methacrylic copolymer is preferably 25% by mass or more, more preferably 25% by mass, based on 100% by mass of all structural units. 0 to 99.5% by mass, more preferably 30.0 to 99.3% by mass, particularly preferably 40.0 to 99.0% by mass. Using 25.0% by mass or more is preferable from the viewpoint of low dielectric constant and low dielectric loss in a high frequency band.
- the methacrylic copolymer contains a crosslinkable functional group-containing (meth)acrylate compound having a crosslinkable functional group in the ester portion, it is crosslinked to increase the gel fraction when a crosslinking agent is used, It becomes easier to obtain excellent anti-foaming and peeling properties. Moreover, since it becomes easy to obtain favorable cohesive force, it becomes easy to obtain strong adhesiveness. Furthermore, it becomes easy to suppress the whitening of the adhesive sheet that occurs in a high-humidity environment.
- the crosslinkable functional group possessed by the (meth)acrylate compound containing the crosslinkable functional group is, for example, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group such as a glycidyl group, since the gel fraction can be easily adjusted. containing groups, isocyanate groups, aziridyl groups, and the like. Among them, a hydroxyl group is preferable because the gel fraction can be easily adjusted.
- the crosslinkable functional group-containing (meth)acrylate compound can be used alone or in combination of two or more.
- Examples of the (meth)acrylate compound containing a crosslinkable functional group having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic acid hydroxylauryl, 4-hydroxymethylcyclohexyl (meth)acrylate and the like.
- 2-hydroxyethyl (meth)acrylate is preferable from the viewpoint that good cohesive force can be easily obtained and adhesion reliability at high temperatures can be easily obtained.
- the content of the crosslinkable functional group-containing (meth)acrylate compound in the methacrylic copolymer according to the present invention is preferably 0.1 to 30.0% by mass with respect to 100% by mass of all structural units, More preferably 0.2 to 20.0% by mass, still more preferably 0.3 to 10.0% by mass, and particularly preferably 0.5 to 5.0% by mass. It is preferable to use 0.1% by mass or more from the viewpoint of adjusting the gel fraction, and to use 30.0% by mass or less is preferable from the viewpoint of low dielectric constant and low dielectric loss in a high frequency band.
- the methacrylic copolymer may contain a copolymerizable monomer in addition to the methacrylate compound having a hydrocarbon group of 6 or more carbon atoms and the crosslinkable functional group-containing (meth)acrylate compound.
- a copolymerizable monomer can be used individually or in combination of 2 or more types.
- Examples of the copolymerizable monomer include, for example, an acrylate compound having a hydrocarbon group having 1 to 24 carbon atoms, a methacrylate compound having a hydrocarbon group having 1 to 5 carbon atoms, and a repeating unit of the main chain in which all carbon atoms are side chains.
- the adhesive composition of the present invention preferably does not contain or substantially does not contain acidic group-containing monomers (eg, carboxyl group-containing monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, etc.).
- This configuration is preferable in that an excellent anti-corrosion effect can be obtained for the antenna element or wiring.
- the content of the acidic group-containing monomer is preferably 0.05% by weight or less (for example, 0 to 0.05% by weight), more preferably 0.01% by weight or less, relative to the total amount of the adhesive composition. (for example, 0 to 0.01% by weight), more preferably 0.001% by weight or less (for example, 0 to 0.001% by weight), can be said to be substantially free.
- heterocyclic-containing monomers carboxyl group-containing monomers, amide group-containing monomers, amino group-containing monomers, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers have an appropriate cohesive force for the adhesive layer. It is preferable in that it is easy to obtain and the 180° peeling adhesive force to a glass plate or an acrylic plate is increased to easily obtain strong adhesiveness, and from the viewpoint of metal corrosion prevention, heterocyclic-containing monomers are more preferable.
- methacrylate compounds having a hydrocarbon group having 1 to 5 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, methacrylate s -butyl, t-butyl methacrylate, isopentyl methacrylate and the like.
- Examples of the acrylate compound having a hydrocarbon group having 1 to 24 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, s-butyl acrylate, acrylic t-butyl acrylate, pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate , dodecyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, h
- the heterocycle-containing monomers include heterocycles having only nitrogen atoms as heteroatoms (pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, pyrimidine, pyrroline, piperazine, pyrazine, etc.), heterocycles having nitrogen and oxygen atoms ( pyrrolidone, oxazole, isoxazole, morpholine, morpholinone, piperidone, lactam, oxazine, morpholinedione, succinimide, itaconimide, etc.), heterocycles containing nitrogen and sulfur atoms (thiazole, isothiazole, thiazine), heterocycles containing oxygen atoms (lactone, tetrahydrofuran, furan, tetrahydropyran, dioxane, etc.), and a heterocyclic ring having a sulfur atom (tetrahydrothiophene, thiophene, te
- the pressure-sensitive adhesive layer can have appropriate flexibility, and excellent stress relaxation and step conformability can be easily obtained. .
- heterocyclic-containing monomers having a heterocyclic ring having only a nitrogen atom as the heteroatom include N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, and N-vinylpyrrole. , N-vinylimidazole, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylpyrazole and the like.
- heterocyclic ring-containing monomer having a heterocyclic ring having a nitrogen atom and an oxygen atom as the heteroatom examples include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-(meth)acryloyl-2-pyrrolidone, N -vinyloxazole, N-vinylisoxazole, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide , N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyhexamethylenesucc
- heterocyclic-containing monomer having a heterocyclic ring containing a nitrogen atom and a sulfur atom as the heteroatom examples include N-vinylthiazole and N-vinylisothiazole.
- N-vinyl-2-pyrrolidone is particularly preferred.
- carboxyl group-containing monomer examples include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- the carboxyl group-containing monomers also include, for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride. Alternatively, it may be a derivative formed by ester bonding with, for example, itaconic acid.
- nitrile group-containing monomer examples include (meth)acrylonitrile.
- Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate.
- amide group-containing monomer examples include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl N,N-dialkyl (meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl ( N-alkyl(meth)acrylamides such as meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic acids such as N-vinylacetamide Amides; monomers having a hydroxyl group and an amide group, such as N-(2-hydroxyethyl) (meth)
- the (meth)acrylamides also include, for example, various N-alkoxyalkyl(meth)acrylamides, such as N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and the like. .
- amino group-containing monomer examples include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, and the like.
- Examples of the (meth)acrylic acid alkoxyalkyl ester having an alkoxy group having 5 or less carbon atoms include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxy (meth)acrylate. triethylene glycol, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate and the like.
- Examples of the sulfonic acid group-containing monomer include sodium vinyl sulfonate.
- the above macromonomer is a high-molecular-weight monomer obtained by polymerizing a plurality of the above monomer components.
- a macromonomer When a macromonomer is used, structural units derived from monomer components constituting the macromonomer are present continuously to some extent in the base polymer. Therefore, by using a macromonomer, it is possible to introduce a higher-order structure derived from the macromonomer into the base polymer, and the properties required for adhesives (adhesive strength, cohesive strength, step conformability, etc.) can be easily achieved. can be adjusted.
- the weight average molecular weight of the macromonomer is preferably 3,000 to 35,000, more preferably 4,000 to 30,000, still more preferably 5,000 to 25,000, and particularly preferably 6,000 to 20,000.
- polyfunctional monomer having two or more polymerizable functional groups examples include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, Tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, polyester acrylate, urethane acrylate and the like.
- a polyfunctional monomer can be used individually or in combination of 2 or more types.
- the content of the polyfunctional monomer in the methacrylic copolymer according to the present invention is not particularly limited, but is 0.5% by mass or less (for example, 0 to 0.5 % by mass), more preferably 0 to 0.35 mass %, still more preferably 0 to 0.2 mass %.
- the content of the polyfunctional monomer is 0.5% by mass or less, the pressure-sensitive adhesive layer has appropriate cohesive strength, and the pressure-sensitive adhesive strength and step absorbability are easily improved, which is preferable.
- the polyfunctional monomer may not be used, but the content of the polyfunctional monomer when the cross-linking agent is not used is preferably 0.001 to 0.5% by mass. , more preferably 0.001 to 0.35% by mass, more preferably 0.002 to 0.2% by mass.
- the total content of the copolymerizable monomers in the methacrylic copolymer is not particularly limited, but is preferably 30.0% by mass or less, more preferably 15.0% by mass, based on 100% by mass of all structural units. It is 0% by mass or less.
- the methacrylic copolymer is obtained by mixing the methacrylate compound having a hydrocarbon group with 6 or more carbon atoms, the crosslinkable functional group-containing (meth)acrylate compound and the copolymerizable monomer, or by a known or conventional polymerization method. It can be obtained by polymerizing with Examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method using active energy ray irradiation (active energy ray polymerization method). Among them, the solution polymerization method and the active energy ray polymerization method are preferable, and the active energy ray polymerization method is more preferable, from the viewpoints of the transparency, water resistance, cost, etc. of the pressure-sensitive adhesive layer.
- Examples of the active energy ray irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as ⁇ -ray, ⁇ -ray, ⁇ -ray, neutron beam, and electron beam, and ultraviolet rays, particularly ultraviolet rays. is preferred.
- the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause the reaction of the monomer components.
- solvents may be used in the polymerization of the methacrylic copolymer.
- examples of such solvents include esters (ethyl acetate, n-butyl acetate, etc.), aromatic hydrocarbons (toluene, benzene, etc.), aliphatic hydrocarbons (n-hexane, n-heptane, etc.), Organic solvents such as alicyclic hydrocarbons (cyclohexane, methylcyclohexane, etc.) and ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.) can be mentioned.
- a solvent can be used individually or in combination of 2 or more types.
- a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- the photopolymerization initiator is not particularly limited. Active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like can be mentioned.
- a photoinitiator can be used individually or in combination of 2 or more types.
- benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisole methyl ether and the like.
- acetophenone-based photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone.
- Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. be done.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
- Examples of the benzoin-based photopolymerization initiator include benzoin.
- Examples of the benzyl-based photopolymerization initiator include benzyl.
- benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
- ketal-based photopolymerization initiator examples include benzyl dimethyl ketal.
- thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
- the amount of the photopolymerization initiator used is not particularly limited. 0.01 to 5.0 parts by mass.
- thermal polymerization initiator examples include azo polymerization initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox polymerization initiators, and the like. .
- the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
- the azo polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), 2,2'-azobis (2- methyl propionate), 4,4′-azobis-4-cyanovaleric acid and the like.
- the amount of the thermal polymerization initiator used is preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of all structural units of the methacrylic copolymer. More preferably, it is 0.1 to 0.3 parts by mass.
- the weight average molecular weight (Mw) of the copolymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, and still more preferably 300,000 to 3,000,000.
- a configuration in which the weight-average molecular weight is 100,000 or more is preferable in terms of improving adhesive strength and holding properties, and improving resistance to foaming and peeling.
- a configuration in which the weight-average molecular weight is 5,000,000 or less is preferable in terms of easily increasing adhesive strength and improving resistance to foaming and peeling.
- the weight-average molecular weight (Mw) of the copolymer can be determined by GPC in terms of polystyrene. For example, it can be measured under the following conditions using a high-speed GPC device (product name “HPLC-8120GPC” manufactured by Tosoh Corporation). Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min
- the glass transition temperature (Tg) of the copolymer is preferably -70 to 100°C, more preferably -65 to 50°C, still more preferably -60 to 10°C.
- Tg glass transition temperature
- the glass transition temperature of the methacrylic copolymer is ⁇ 70° C. or higher, the cohesive force is improved, and the resistance to foaming and peeling is easily improved, which is preferable.
- the glass transition temperature is 100 ° C. or less, the pressure-sensitive adhesive composition has moderate flexibility, and it becomes easy to obtain good adhesive strength and good step absorbability, and it is easy to obtain excellent adhesion reliability. Therefore, it is preferable.
- the glass transition temperature (Tg) of the above copolymer is the glass transition temperature (theoretical value) represented by the following FOX formula.
- Tg is the glass transition temperature (unit: K) of the copolymer
- Tg is the glass transition temperature (unit: K) when monomer i forms a homopolymer
- W is the monomer component of monomer i .
- Tg of the homopolymer of the monomers constituting the above copolymer the following values can be adopted. ⁇ Lauryl methacrylate -65°C ⁇ 2-Ethylhexyl methacrylate -10°C ⁇ Lauryl acrylate 0°C ⁇ 2-Ethylhexyl acrylate -70°C ⁇ Isodecyl methacrylate -41°C ⁇ 2-Hydroxyethyl methacrylate 55°C ⁇ Methyl methacrylate 105°C ⁇ Cyclohexyl methacrylate 66°C ⁇ Isobornyl methacrylate 173°C ⁇ Dicyclopentanyl methacrylate 175°C ⁇ Methacrylic acid 228°C ⁇ N-vinylpyrrolidone 86°C ⁇ 2-Phenoxyethyl methacrylate 5°C ⁇ Benzyl methacrylate 54°C ⁇ 2-(2-(2-
- Tg of homopolymers of monomers not described above the values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. Furthermore, as the Tg of a homopolymer of a monomer not described in the above literature, the value obtained by the above-described measuring method (tan ⁇ peak top temperature by viscoelasticity test) can be employed.
- a chain transfer agent may be used in the polymerization of the methacrylic copolymer to adjust the molecular weight.
- the chain transfer agent include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate,
- a chain transfer agent can be used individually or in combination of 2 or more types.
- the content of the chain transfer agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and still more preferably 100 parts by mass of the total structural units of the methacrylic copolymer. 0.3 to 10 parts by mass.
- a methacrylic copolymer having a weight-average molecular weight controlled to 1,000 to 30,000 can be easily obtained by setting the content (the amount used) of the chain transfer agent within the above range.
- the adhesive composition of the present invention preferably contains a cross-linking agent.
- the pressure-sensitive adhesive composition contains a cross-linking agent, the base polymer is cross-linked to increase the gel fraction, thereby making it easier to improve the resistance to foaming and peeling.
- cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal Examples include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents.
- isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable, and isocyanate-based cross-linking agents are more preferable, from the viewpoint of improving resistance to foaming and peeling.
- a crosslinking agent can be used individually or in combination of 2 or more types.
- isocyanate-based crosslinking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate; , cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate , xylylene diisocyanate and other aromatic polyisocyanates.
- lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate
- cyclopentylene diisocyanate cycl
- isocyanate-based cross-linking agent examples include trimethylolpropane/tolylene diisocyanate adduct (trade name "Coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (trade name Commercially available products such as "Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.” and trimethylolpropane/xylylene diisocyanate adduct (trade name "Takenate D-110N” manufactured by Mitsui Chemicals, Inc.) can also be used.
- epoxy-based cross-linking agent examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether , glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
- the content of the cross-linking agent in the adhesive composition is, for example, preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the methacrylic copolymer. be.
- the content of the cross-linking agent is 0.001 parts by mass or more, the resistance to foaming and peeling is easily improved, which is preferable.
- the content of the cross-linking agent is 10 parts by mass or less, the pressure-sensitive adhesive layer has appropriate flexibility and the pressure-sensitive adhesive strength is easily improved, which is preferable.
- the adhesive composition of the present invention contains inorganic fine particles, organic fine particles, and polymer materials other than the base polymer, in addition to the above-mentioned base polymer, from the viewpoint of further lowering the dielectric constant and the dielectric loss in a high frequency band. You can stay. These can be used individually or in combination of 2 or more types. From the viewpoint of low dielectric constant and low dielectric loss in a high frequency band, the above inorganic fine particles and organic fine particles are preferably those exhibiting insulating properties (insulating filler).
- inorganic fine particles examples include metal oxides such as silica, alumina, zirconia, and titania; metal salts such as aluminum borate and aluminum hydroxide; minerals such as mica; and hollow nanosilica. and inorganic fine particles having a hollow structure. These can be used individually or in combination of 2 or more types.
- the inorganic fine particles may be surface-treated from the viewpoint of dispersibility in the base polymer.
- the surface treatment agent known or commonly used agents can be used without limitation, and examples thereof include silane coupling agents, titanium coupling agents, organic acids, polyols, and silicones, with silane coupling agents being preferred.
- Silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, vinyl-tris(2-methoxy)silane, vinyltri Acetoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxy-propylmethyldimethoxysilane, triethoxyphenylsilane, trimethoxyphenylsilane, dimethoxysilane diphenylsilane, methyldiethoxyphenylsilane, dimethoxymethylphenylsilane and the like.
- the particle diameter (D50) of the inorganic fine particles is preferably 1 to 100 nm, more preferably 5 to 80 nm, and more preferably 5 to 80 nm, from the viewpoints of low dielectric constant, low dielectric loss, and transparency in a high frequency band of the pressure-sensitive adhesive composition. It is preferably 10 to 50 nm.
- the median particle size means the particle size (median size) at 50% of the integrated value in the particle size distribution measured by the laser diffraction/scattering method.
- the content thereof is 100 parts by mass of the above-mentioned base polymer from the viewpoints of low dielectric constant, low dielectric loss and transparency in a high frequency band of the pressure-sensitive adhesive composition. is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, more preferably 0.1 to 20 parts by mass, still more preferably 0.15 to 10 parts by mass, particularly preferably 0.2 to 5 parts by mass.
- organic fine particles examples include styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride resins, vinylidene chloride resins, amide resins, and urethane.
- Polymers such as resins, phenolic resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefinic resins, and fluorine-based resins, or fine particles composed of crosslinked products of these polymers, and further these polymers, Examples thereof include fine particles configured to have a hollow structure by means of a crosslinked polymer. These can be used individually or in combination of 2 or more types.
- the particle size (D50) of the organic fine particles is preferably 1 to 100 nm, more preferably 5 to 80 nm, and more preferably 5 to 80 nm, from the viewpoints of low dielectric constant, low dielectric loss, and transparency in the high frequency band of the pressure-sensitive adhesive composition. It is preferably 10 to 50 nm.
- the above median particle diameter means the particle diameter (median diameter) at an integrated value of 50% in the particle size distribution measured by the laser diffraction/scattering method.
- the content thereof is 100 parts by mass of the above-mentioned base polymer from the viewpoint of low dielectric constant, low dielectric loss and transparency in a high frequency band of the pressure-sensitive adhesive composition. is usually 0.01 to 30 parts by mass, preferably 0.05 to 25 parts by mass, more preferably 0.1 to 20 parts by mass, more preferably 0.15 to 10 parts by mass, particularly preferably is 0.2 to 5 parts by mass.
- polymer material As the polymer material that can be blended in the pressure-sensitive adhesive composition of the present invention, those having low dielectric constant and dielectric loss and compatibility with the base polymer are preferable. , polyethylene, polypropylene, polystyrene, polycarbonate, norbornene resin or addition copolymer resin with olefins, polyphenylene ether, bismaleimide/triazine/resin, polyetherimide, polyimide, polyetheretherketone (PEEK), liquid crystal polymer, Rubber/elastomers, hydrogenated polyolefin resins, terpenes, isoprenes, terpene phenol resins, aromatic modified terpene resins and their hydrogenated resins, and the like. These can be used individually or in combination of 2 or more types.
- the pressure-sensitive adhesive composition of the present invention contains a polymer material
- its content is not particularly limited. It is usually 0.01 to 50 parts by mass, preferably 0.05 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the base polymer.
- the pressure-sensitive adhesive composition of the present invention may further contain an antirust agent. If the pressure-sensitive adhesive composition contains a rust inhibitor, it is preferable in that an excellent anti-corrosion effect can be obtained for the antenna element and metal wiring.
- a rust inhibitor is a compound that prevents metal from rusting and corroding.
- rust inhibitors include amine compounds, benzotriazole compounds, and nitrites. Others include ammonium benzoate, ammonium phthalate, ammonium stearate, ammonium palmitate, ammonium oleate, ammonium carbonate, dicyclohexylamine benzoate, urea, urotropine, thiourea, phenyl carbamate, cyclohexylammonium-N-cyclohexyl. carbamate (CHC) and the like.
- a rust inhibitor can be used individually or in combination of 2 or more types.
- amine compound examples include hydroxy group-containing amine compounds such as 2-amino-2-methyl-1-propanol, monoethanolamine, monoisopropanolamine, diethylethanolamine, ammonia and ammonia water; cyclic amines such as morpholine; cyclohexyl Cyclic alkylamine compounds such as amines; linear alkylamines such as 3-methoxypropylamine; Examples of nitrites include dicyclohexylammonium nitrite (DICHAN), diisopropylammonium nitrite (DIPAN), sodium nitrite, potassium nitrite, and calcium nitrite.
- DICHAN dicyclohexylammonium nitrite
- DIPAN diisopropylammonium nitrite
- sodium nitrite potassium nitrite
- calcium nitrite examples include calcium nitrite.
- the content of the rust inhibitor is preferably 0.02 to 15 parts by mass with respect to 100 parts by mass of the methacrylic copolymer.
- the content is 0.02 parts by mass or more, good corrosion prevention performance can be easily obtained, which is preferable.
- the content is 15 parts by mass or less, transparency is easily ensured, and adhesion reliability such as resistance to foaming and peeling is easily ensured, which is preferable.
- the rust preventive agent can provide adhesion reliability, transparency, and corrosion resistance to the methacrylic copolymer at a high level in a well-balanced manner, and can provide excellent appearance. Therefore, benzotriazole compounds are preferred.
- the benzotriazole-based compound is not particularly limited as long as it is a compound having a benzotriazole skeleton, but from the viewpoint that having a structure represented by the following formula (1) provides a more excellent anti-corrosion effect. preferable.
- R 1 and R 2 are the same or different, and R 1 is a substituent on the benzene ring, which is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 14 carbon atoms, amino group, mono- or di-C 1-10 alkylamino group, amino-C 1-6 alkyl group, mono- or di-C 1-10 alkylamino-C 1-6 alkyl group , a mercapto group, an alkoxycarbonyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- R 1 may be the same or different, and R 2 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms. group, amino group, mono- or di-C 1-10 alkylamino group, amino-C 1-6 alkyl group, mono- or di-C 1-10 alkylamino-C 1-6 alkyl group, mercapto group, carbon number 1-12 or a substituent such as an alkoxy group having 1 to 12 carbon atoms.
- R 1 is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxycarbonyl group, or the like, and more preferably a methyl group or the like.
- n is preferably 0 or 1.
- R 2 is preferably a hydrogen atom, a mono- or di-C 1-10 alkylamino-C 1-6 alkyl group, etc., a hydrogen atom, a di-C 1-8 alkylamino-C 1-4 alkyl group, etc. is more preferred.
- the content of the benzotriazole-based compound is preferably 0.02 to 3 parts by mass, more preferably 0.02 to 2.5 parts by mass, and still more preferably 0.02 to 0.02 parts by mass with respect to 100 parts by mass of the base polymer. 2 parts by mass.
- amount of the benzotriazole-based compound is within a certain range, adhesion reliability such as resistance to foaming and peeling can be reliably secured, and an increase in haze of the adhesive sheet can be reliably prevented.
- the pressure-sensitive adhesive composition of the invention may further contain a silane coupling agent.
- a silane coupling agent it is preferable because excellent adhesion to glass (especially, excellent adhesion reliability to glass at high temperature and high humidity) can be easily obtained.
- silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane, and the like. Among them, ⁇ -glycidoxypropyltrimethoxysilane is preferred.
- examples of the silane coupling agent include commercially available products such as the product name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.). A silane coupling agent can be used individually or in combination of 2 or more types.
- the content of the silane coupling agent is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.5 parts by mass with respect to 100 parts by mass of the base polymer, from the viewpoint of improving adhesion reliability to glass. part by mass.
- the pressure-sensitive adhesive composition of the present invention may optionally contain antioxidants, cross-linking accelerators, tackifying resins (rosin derivatives, polyterpene resins, oil-soluble phenols, etc.), aging Known additives such as inhibitors, colorants (pigments, dyes, etc.), ultraviolet absorbers, chain transfer agents, plasticizers, softeners, surfactants, and antistatic agents may be included. These can be used individually or in combination of 2 or more types.
- the content thereof is preferably 0.01 parts by mass or more, more preferably 0.01 part by mass or more based on 100 parts by mass of the base polymer, from the viewpoint of imparting appropriate adhesiveness. is 0.05 parts by mass or more. Also, from the point of avoiding excessively high peel strength, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
- the pressure-sensitive adhesive layer of the present invention Since the pressure-sensitive adhesive layer of the present invention is formed from the pressure-sensitive adhesive composition of the present invention, it exhibits a low dielectric constant and low dielectric loss in millimeter waves in a high frequency band (28 to 60 GHz). That is, the pressure-sensitive adhesive layer of the present invention can suppress radiation loss of millimeter waves.
- the pressure-sensitive adhesive layer of the present invention is preferable in that it has a low dielectric constant at 28 GHz and can suppress radiation loss of millimeter waves.
- the dielectric constant of the adhesive layer of the present invention at a frequency of 28 GHz is preferably 2.0 to 5.0, more preferably 2.05 to 4.5, still more preferably 2.1 to 4.0, still more preferably 2.0. 15 to 3.5, more preferably 2.2 to 3.4, more preferably 2.2 to 3.3, more preferably 2.2 to 3.2, more preferably 2.2 to 3.1, More preferably 2.2 to 3.0, particularly preferably 2.2 to 2.9.
- the dielectric constant at 28 GHz of the pressure-sensitive adhesive layer of the present invention can be adjusted by adjusting the type of base polymer, monomer composition, type and content of additives, etc. that constitute the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. , can be adjusted.
- the pressure-sensitive adhesive layer of the present invention is preferable in that the dielectric loss at 28 GHz is controlled to be low and the radiation loss of millimeter waves can be suppressed.
- the dielectric loss of the adhesive layer of the present invention at a frequency of 28 GHz is preferably 0.050 or less, more preferably 0.045 or less, still more preferably 0.040 or less, still more preferably 0.035 or less, and even more preferably 0.045 or less. 030 or less, particularly preferably 0.025 or less, most preferably 0.020 or less.
- the lower limit is not particularly limited, it is preferably 0.0001 or more, and may be 0.0005 or more or 0.0010 or more.
- the dielectric loss at 28 GHz in the pressure-sensitive adhesive layer of the present invention can be adjusted by adjusting the type of base polymer, monomer composition, type and content of additives, etc. that constitute the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. , can be adjusted.
- the adhesive layer of the present invention is preferable in that it has a low dielectric constant at 60 GHz and can suppress radiation loss of millimeter waves.
- the dielectric constant of the adhesive layer of the present invention at a frequency of 60 GHz is preferably 2.0 to 5.0, more preferably 2.1 to 4.5, still more preferably 2.2 to 4.0, still more preferably 2 .2 to 3.5, more preferably 2.2 to 3.4, more preferably 2.2 to 3.3, more preferably 2.2 to 3.2, more preferably 2.2 to 3.1 , more preferably 2.2 to 3.0, and particularly preferably 2.2 to 2.9.
- the dielectric constant at 60 GHz in the pressure-sensitive adhesive layer of the present invention can be adjusted by adjusting the type of base polymer, monomer composition, type and content of additives, etc. that constitute the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. , can be adjusted.
- the pressure-sensitive adhesive layer of the present invention preferably has a controlled low dielectric loss at 60 GHz, which is preferable in that it can suppress the radiation loss of millimeter waves.
- the dielectric loss of the pressure-sensitive adhesive layer of the present invention at a frequency of 60 GHz is preferably 0.050 or less, more preferably 0.045 or less, still more preferably 0.040 or less, still more preferably 0.035 or less, and even more preferably 0. 0.030 or less, particularly preferably 0.025 or less, most preferably 0.020 or less.
- the lower limit of dielectric loss at a frequency of 60 GHz is preferably 0.0001 or more, and may be 0.0005 or more or 0.0010 or more.
- the dielectric loss at 60 GHz in the pressure-sensitive adhesive layer of the present invention can be determined by adjusting the type of base polymer, monomer composition, type and content of additives, etc. that constitute the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. , can be adjusted.
- the adhesive layer of the present invention is preferably transparent or has transparency. Therefore, the visibility and appearance through the pressure-sensitive adhesive composition are excellent. Thus, the pressure-sensitive adhesive layer of the present invention is suitable for optical applications.
- the haze (according to JIS K7136) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 1.2% or less, more preferably 1.1% or less, still more preferably 1.0% or less, and still more preferably It is 0.9% or less, particularly preferably 0.8% or less.
- the haze is measured, for example, by setting the pressure-sensitive adhesive layer to a thickness of 25 ⁇ m, allowing it to stand at normal conditions (23° C., 50% RH) for at least 24 hours, and applying it to a slide glass (for example, a total light transmittance of 91.8% and a haze of 0.8%). 4%) can be used as a sample and measured using a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory).
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive layer of the present invention is preferably 85% or more, more preferably 88% or more, still more preferably 89% or more, and still more preferably 90%. % or more, more preferably 91% or more, and particularly preferably 92% or more.
- the total light transmittance is 85% or more, excellent transparency and excellent appearance are likely to be obtained.
- the pressure-sensitive adhesive layer thickness is 25 ⁇ m, and after this is left to stand at normal conditions (23° C., 50% RH) for at least 24 hours, if a separator is provided, it is peeled off, and a slide glass (for example, the total light transmittance of 91.8%, haze of 0.4%) is used as a sample, and a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory) is used. can be measured.
- HM-150 manufactured by Murakami Color Research Laboratory
- the haze and total light transmittance of the pressure-sensitive adhesive layer of the present invention can be adjusted by adjusting the monomer composition, the type and content of additives, and the like.
- the gel fraction (percentage of insoluble components) of the pressure-sensitive adhesive layer of the present invention is preferably 30 to 95%, more preferably 35 to 90%, still more preferably 40 to 85%, still more preferably 45 to 80%, Especially preferred is 50 to 75%.
- the cohesive force of the pressure-sensitive adhesive layer is improved, dents are less likely to occur during handling, and foaming or peeling occurs at the interface with the adherend in a high-temperature environment. is suppressed, and excellent anti-foaming and peeling resistance is easily obtained, which is preferable.
- the gel fraction is 95% or less, it is preferable because a suitable flexibility can be obtained, the adhesiveness and step followability are further improved, and foreign substances are hardly absorbed.
- the gel fraction (ratio of solvent-insoluble components) can be calculated, for example, as follows.
- the gel fraction of the pressure-sensitive adhesive layer of the present invention can be controlled by, for example, monomer composition, weight average molecular weight, amount of cross-linking agent used, types and amounts of other additives used, and the like.
- the storage modulus of the pressure-sensitive adhesive layer of the present invention at 25° C. is preferably 0.01 MPa or more, more preferably 0.02 MPa or more, still more preferably 0.03 MPa or more, still more preferably 0.04 MPa or more, and still more preferably 0. 0.05 MPa or more, particularly preferably 0.10 MPa or more.
- the storage elastic modulus is 0.01 MPa or more, dents are less likely to occur during handling, and good adhesion reliability can be easily obtained, which is preferable.
- the storage elastic modulus of the pressure-sensitive adhesive layer is measured by dynamic viscoelasticity at a frequency of 1 Hz.
- the above storage modulus is the real part of the shear modulus represented by a complex number, and the tensile modulus can be converted in consideration of the Poisson's ratio of the sample.
- the storage elastic modulus of the pressure-sensitive adhesive layer of the present invention can be controlled by the monomer composition, weight-average molecular weight, amount of cross-linking agent used (added amount), types and amounts of other additives used, and the like.
- the 300% tensile residual stress of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 2 to 24 N/cm 2 , more preferably 2.5 to 20 N/cm 2 , still more preferably 3 to 16 N/cm 2 . cm2 .
- the 300% tensile residual stress is 2 N/cm 2 or more, good resistance to foaming and peeling is likely to be obtained, and when it is 24 N/cm 2 or less, good stress relaxation is obtained and good conformability to unevenness is obtained. is easy to obtain, which is preferable.
- the pressure-sensitive adhesive layer of the present invention can easily obtain excellent stress relaxation properties and can easily exhibit excellent step conformability. , for example, a height of 20 to 50 ⁇ m).
- the 300% tensile residual stress was measured at 23°C and 50%R. H. Under the environment of , pull the adhesive layer in the length direction to 300% elongation (strain), hold the elongation, and determine the tensile load applied to the adhesive layer 300 seconds after the end of pulling, It is the value (N/cm 2 ) obtained by dividing the tensile load by the initial cross-sectional area (cross-sectional area before pulling) of the pressure-sensitive adhesive layer. The initial elongation of the adhesive layer is 100%.
- the 300% tensile residual stress of the pressure-sensitive adhesive layer of the present invention can be controlled by the monomer composition of the base polymer, the weight average molecular weight, the amount (addition amount) of the cross-linking agent used, and the type and amount of other additives used. .
- H. is preferably 430 g/m 2 /day or less, more preferably 300 g/m 2 /day or less, still more preferably 250 g/m 2 /day or less, still more preferably 200 g/m 2 /day or less, still more preferably is 150 g/m 2 /day or less, more preferably 100 g/m 2 /day or less, still more preferably 50 g/m 2 /day or less, and particularly preferably 30 g/m 2 /day or less.
- the lower limit of water vapor permeability is not particularly limited, but may be, for example, 10 g/m 2 /day or more, 20 g/m 2 /day or more, or 25 g/m 2 /day or more.
- the water vapor transmission rate (WVTR) is a value measured based on the cup method.
- the adhesive layer of the present invention exhibits low water vapor permeability. This is because it has a surface with excellent water resistance, and as a result, the moisture absorption rate inside the pressure-sensitive adhesive layer can be reduced. Furthermore, since the amount of change in dielectric loss due to moisture absorption is controlled to be low, millimeter-wave radiation loss can be suppressed.
- the change in dielectric loss of the pressure-sensitive adhesive layer of the present invention at a frequency of 28 GHz is preferably 0.006 or less, more preferably 0.005 or less, and still more preferably 0.004 or less.
- the lower limit of the amount of change in dielectric loss is not particularly limited, but may be, for example, 0.0001 or more, 0.0002 or more, or 0.0003 or more.
- the change in dielectric loss of the pressure-sensitive adhesive layer of the present invention due to moisture absorption at a frequency of 60 GHz is preferably 0.003 or less, more preferably 0.002 or less, and still more preferably 0.001 or less.
- the lower limit of the amount of change in dielectric loss is not particularly limited. , 0.0007 or more, 0.0008 or more, or 0.0009 or more.
- the pressure-sensitive adhesive layer of the present invention has a controlled low saturated moisture absorption rate, it is possible to suppress the radiation loss of millimeter waves. 25° C., 90% R.I. of the pressure-sensitive adhesive layer of the present invention.
- H. is preferably 2.8% or less, more preferably 2.7% or less, still more preferably 2.6% or less, particularly preferably 2.5% or less, 2.4% or less, .3% or less, 2.2% or less, 2.1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5 % or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less , or 0.6% or less.
- the saturated moisture absorption rate of H is low, it is possible to suppress the radiation loss of millimeter waves near room temperature.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.3% or more, 0.4% or more, or 0.5% or more.
- H. is preferably 2.8% or less, more preferably 2.6% or less, still more preferably 2.4% or less, particularly preferably 2.3% or less, and 2.2% or less .1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% % or less, 1.2% or less, 1.1% or less, 1.0% or less, 0.9% or less, 0.8% or less, or 0.7% or less.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.4% or more, 0.5% or more, or 0.6% or more. 65°C, 90% R.I.
- the saturated moisture absorption rate in is preferably 5.0% or less, more preferably 4.0% or less, still more preferably 3.5% or less, particularly preferably 3.0% or less, 2.8% or less, 2 .6% or less, 2.4% or less, 2.2% or less, 2.0% or less, 1.8% or less, 1.6% or less, 1.4% or less, 1.2% or less, 1.0 % or less, or 0.8% or less.
- the lower limit of the saturated moisture absorption rate is not particularly limited, but may be, for example, 0.4% or more, 0.5% or more, or 0.6% or more.
- the dielectric constant or dielectric loss at 28 GHz or 60 GHz, the water vapor permeability, the amount of change in dielectric loss due to moisture absorption, and the saturated moisture absorption rate of the adhesive layer of the present invention can be adjusted by adjusting the monomer composition, the type and content of additives, etc. , can be adjusted.
- the thickness of the pressure-sensitive adhesive layer of the present invention is not particularly limited, it is preferably 10-500 ⁇ m, more preferably 11-400 ⁇ m, even more preferably 12-350 ⁇ m, and particularly preferably 12-300 ⁇ m.
- the thickness is at least a certain value, the conformability to irregularities and the adhesion reliability are likely to be improved.
- the thickness is below a certain value, foreign matter is less likely to be absorbed during handling, and there is a tendency for excellent manufacturability.
- the method for producing the pressure-sensitive adhesive layer is not particularly limited. It is mentioned that Curing can be performed by irradiation with active energy rays, drying by heating, or the like.
- a known coating method may be used for applying (coating) the pressure-sensitive adhesive composition.
- coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters may be used.
- the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it has the pressure-sensitive adhesive layer of the present invention.
- the pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet in which both sides are pressure-sensitive adhesive layer surfaces, or may be a single-sided pressure-sensitive adhesive sheet in which only one side is pressure-sensitive adhesive layer surfaces. Among them, a double-sided pressure-sensitive adhesive sheet is preferable from the viewpoint of bonding two members together.
- the term "adhesive sheet” includes a tape-like one, that is, “adhesive tape”.
- the adhesive layer surface may be called an "adhesive surface.”
- the pressure-sensitive adhesive sheet of the present invention may have a separator (release liner) provided on the pressure-sensitive adhesive surface until use.
- the pressure-sensitive adhesive sheet of the present invention may be a so-called “base-less type” pressure-sensitive adhesive sheet (hereinafter sometimes referred to as “base-less pressure-sensitive adhesive sheet”) that does not have a base material (base layer). , a pressure-sensitive adhesive sheet having a substrate (hereinafter sometimes referred to as a “substrate-attached pressure-sensitive adhesive sheet").
- base-less pressure-sensitive adhesive sheet a pressure-sensitive adhesive sheet having a substrate
- substrate-less pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet consisting only of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer and a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer (sometimes referred to as "another pressure-sensitive adhesive layer”). ) and the like.
- the pressure-sensitive adhesive sheet with a substrate includes a pressure-sensitive adhesive sheet having the above pressure-sensitive adhesive layer on at least one side of a substrate.
- a substrate-less pressure-sensitive adhesive sheet (substrate-less double-sided pressure-sensitive adhesive sheet) is preferable, and a substrate-less double-sided pressure-sensitive adhesive sheet consisting only of the above pressure-sensitive adhesive layer is more preferable.
- a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer on both sides of a substrate double-sided pressure-sensitive adhesive sheet with substrate is also preferable.
- the pressure-sensitive adhesive layers on both sides of the double-sided pressure-sensitive adhesive sheet with a substrate may be the pressure-sensitive adhesive layers of the present invention, or one side may be the pressure-sensitive adhesive layer of the present invention and the other side may be another pressure-sensitive adhesive layer. good too.
- base material base material layer
- the pressure-sensitive adhesive sheet of the present invention is preferably a base-less pressure-sensitive adhesive sheet in order to avoid radiation loss of millimeter waves due to the base material.
- the base material is made of a material with a low dielectric constant and low dielectric loss, it may be a pressure-sensitive adhesive sheet with a base material. Since it is desirable that the base material can be used regardless of the polarization state of millimeter waves, non-stretched base materials, particularly isotropic base materials, are preferred.
- the 180° peeling adhesive strength of the adhesive sheet of the present invention to a glass plate at a tensile speed of 300 mm / min is although it is not limited, it is preferably 3 N/20 mm or more, more preferably 3.5 N/20 mm or more, still more preferably 4 N/20 mm or more, and still more preferably 4 N/20 mm or more from the viewpoint that sufficient adhesion to the antenna element can be obtained if the adhesive strength is high.
- the upper limit of the 180° peeling adhesive strength of the pressure-sensitive adhesive sheet of the present invention to a glass plate at a tensile speed of 300 mm/min is not particularly limited, but for example, it is preferably 30 N/20 mm or less, more preferably 25 N/20 mm or less.
- the 180° peeling adhesive strength against a glass plate at a tensile speed of 300 mm/min is determined by the following method for measuring 180° peeling adhesive strength.
- glass plate examples include the product name "Soda Lime Glass #0050” (manufactured by Matsunami Glass Industry Co., Ltd.). In addition, non-alkali glass, chemically strengthened glass, and the like can also be used.
- the 180° peeling adhesive strength at a tensile speed of 300 mm/min against the glass plate is obtained by the following measuring method.
- the adhesive surface of the adhesive sheet was adhered to the adherend and pressed under the conditions of one reciprocating press with a 2 kg roller, and the adhesive sheet was pressed at 23° C. and 50% R.I. H. After aging for 30 minutes in an atmosphere of 23°C, 50% R.I. H.
- the pressure-sensitive adhesive sheet is peeled off from the adherend under conditions of a peeling speed of 300 mm/min and a peeling angle of 180° in an atmosphere of , and the 180° peeling adhesive strength (N/20 mm) is measured.
- the 180° peeling adhesive strength of the adhesive sheet of the present invention depends on the monomer composition of the base polymer (acrylic polymer), the weight average molecular weight, the amount of cross-linking agent used (addition amount), the type and amount of other additives used, etc. can be controlled.
- the thickness (total thickness) of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 10-500 ⁇ m, more preferably 11-400 ⁇ m, still more preferably 12-350 ⁇ m, and particularly preferably 12-300 ⁇ m. When the thickness is equal to or greater than a certain value, peeling at the step portion is less likely to occur. Further, when the thickness is below a certain level, it becomes easier to maintain an excellent appearance during production. Note that the thickness of the pressure-sensitive adhesive sheet of the present invention does not include the thickness of the separator.
- the haze (according to JIS K7136) of the adhesive sheet of the present invention is not particularly limited, but is preferably 1.2% or less, more preferably 1.1% or less, still more preferably 1.0% or less, and still more preferably 0%. 0.9% or less, particularly preferably 0.8% or less.
- the haze is measured, for example, by setting the pressure-sensitive adhesive layer to a thickness of 25 ⁇ m, allowing it to stand at normal conditions (23° C., 50% RH) for at least 24 hours, and applying it to a slide glass (for example, a total light transmittance of 91.8% and a haze of 0.8%). 4%) can be used as a sample and measured using a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory).
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive sheet of the present invention is preferably 85% or more, more preferably 88% or more, still more preferably 89% or more, and still more preferably 90%. above, more preferably 91% or more, particularly preferably 92% or more. When the total light transmittance is 85% or more, excellent transparency and excellent appearance are likely to be obtained.
- the pressure-sensitive adhesive layer thickness is 25 ⁇ m, and after this is left to stand at normal conditions (23° C., 50% RH) for at least 24 hours, if a separator is provided, it is peeled off, and a slide glass (for example, the total light transmittance of 91.8%, haze of 0.4%) is used as a sample, and a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory) is used. can be measured.
- HM-150 manufactured by Murakami Color Research Laboratory
- the haze and total light transmittance of the pressure-sensitive adhesive layer of the present invention can be adjusted by adjusting the monomer composition, the type and content of additives, and the like.
- the pressure-sensitive adhesive sheet of the present invention is not particularly limited, it is preferably manufactured according to a known or commonly used manufacturing method.
- the pressure-sensitive adhesive sheet of the present invention is a substrate-less pressure-sensitive adhesive sheet, it can be obtained by forming the pressure-sensitive adhesive layer on a separator by the method described above.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate, it may be obtained by directly forming the pressure-sensitive adhesive layer on the surface of the substrate (direct transfer method), or once the pressure-sensitive adhesive layer is formed on the separator. After forming the adhesive layer, the pressure-sensitive adhesive layer may be provided on the substrate by transferring (bonding) to the substrate (transfer method).
- the adhesive sheet of the present invention may have other layers in addition to the adhesive layer.
- examples of other layers include other adhesive layers (adhesive layers other than the above adhesive layer (adhesive layers other than the adhesive layer formed from the adhesive composition of the present invention)), intermediate layers, and undercoats. layers and the like.
- the pressure-sensitive adhesive sheet of the present invention may have two or more other layers.
- the substrate include various optical films such as plastic films, antireflection (AR) films, polarizing plates, and retardation plates.
- plastic films include polyester resins such as polyethylene terephthalate (PET), (meth)acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, and polyarylate.
- polyimide polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer
- trade name "Arton (cyclic olefin polymer, manufactured by JSR Corporation)", trade name “Zeonor (cyclic olefin polymer, Nippon Zeon Co., Ltd.)”
- other plastic materials such as cyclic olefin-based polymers and fluorine-based polymers.
- these plastic materials can be used individually or in combination of 2 or more types.
- the base material On one side or both sides of the base material, it has a known and commonly used single or multiple function such as a hard coat layer, an anti-blocking layer, an antireflection layer, an antistatic layer, an easy adhesion layer, and a moisture-proof layer.
- a surface treatment layer may be appropriately formed.
- the above-mentioned “base material” is a part that is attached to the adherend together with the adhesive layer when the pressure-sensitive adhesive sheet is applied to the adherend.
- a separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the "base material”.
- the base material is preferably transparent.
- the total light transmittance (according to JIS K7361-1) of the base material in the visible light wavelength region is preferably 85% or more, more preferably 88% or more, still more preferably 89% or more, still more preferably 90% or more, More preferably 91% or more, particularly preferably 92% or more.
- the haze of the substrate is preferably 1.0% or less, more preferably 0.8% or less.
- transparent substrates include PET films and non-oriented films such as the trade name "Arton” and the trade name "Zeonor". In particular, a non-oriented film is preferable because its properties do not depend on the direction of the millimeter-wave electric field.
- the thickness of the base material is not particularly limited, it is preferably 12 to 500 ⁇ m, for example.
- the substrate may have either a single-layer structure or a multilayer structure.
- the surface of the substrate may be appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment, plasma treatment and electron beam treatment, and chemical treatments such as undercoating treatment. .
- the pressure-sensitive adhesive sheet of the present invention may have a separator (release liner) provided on the pressure-sensitive adhesive surface until use.
- each pressure-sensitive adhesive surface may be protected by two separators, or a separator having release surfaces on both sides may be used to form a roll. It may be protected in a wound form.
- the separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when applied to an adherend.
- the separator also serves as a support for the pressure-sensitive adhesive layer. Note that the separator does not necessarily have to be provided.
- a commonly used release paper or the like can be used, and is not particularly limited.
- a base material having a release treatment layer a low-adhesive base material composed of a fluoropolymer, a low-adhesive base material composed of a non-polar polymer, and the like can be mentioned.
- substrates having a release treatment layer include plastic films and papers surface-treated with release agents such as silicone, long-chain alkyl, fluorine, and molybdenum sulfide.
- fluorine-based polymer in the low-adhesive substrate made of the fluorine polymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymers.
- non-polar polymer examples include olefin resins (e.g., polyethylene, polypropylene, etc.), and polyester base materials (polyethylene terephthalate base material, polyethylene naphthalate base material, polybutylene terephthalate base material, polybutylene terephthalate base material, etc.). materials, etc.) are also used.
- olefin resins e.g., polyethylene, polypropylene, etc.
- polyester base materials polyethylene terephthalate base material, polyethylene naphthalate base material, polybutylene terephthalate base material, polybutylene terephthalate base material, etc.
- materials, etc. are also used.
- the separator can be formed by a known or commonly used method. Also, the thickness of the separator is not particularly limited.
- the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer of the present invention, it has excellent adhesiveness and resistance to foaming and peeling, and furthermore has excellent stress relaxation properties and excellent conformability to unevenness. Therefore, the adhesion reliability, especially at high temperatures, is excellent. Moreover, it is excellent in external appearance.
- the pressure-sensitive adhesive sheet of the present invention is useful for bonding members that are prone to foaming at the interface at high temperatures.
- polymethyl methacrylate (PMMA) may contain unreacted monomers, and foaming due to foreign matter is likely to occur at high temperatures.
- PC Polycarbonate
- the pressure-sensitive adhesive sheet of the present invention is excellent in resistance to foaming and peeling, it is also useful for plastic adherends containing such resins.
- the pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with a small coefficient of linear expansion, but also for adherends with a large coefficient of linear expansion.
- adherend having a small linear expansion coefficient include a glass plate (linear expansion coefficient of 0.3 ⁇ 10 ⁇ 5 to 0.8 ⁇ 10 ⁇ 5 /° C.), polyethylene terephthalate substrate (PET film, wire expansion coefficient of 1.5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 /° C.).
- PET film polyethylene terephthalate substrate
- wire expansion coefficient of 1.5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 /° C. examples of the adherend having a large coefficient of linear expansion include resin substrates having a large coefficient of linear expansion.
- the pressure-sensitive adhesive sheet of the present invention is useful for bonding an adherend with a small coefficient of linear expansion and an adherend with a large coefficient of linear expansion.
- the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding a glass adherend (for example, a glass plate, chemically strengthened glass, glass lens, etc.) to the resin substrate having a large coefficient of linear expansion.
- the pressure-sensitive adhesive sheet of the present invention is useful for bonding adherends made of various materials, and is particularly useful for bonding glass adherends and plastic adherends.
- the plastic adherend may be an optical film such as a plastic film having an ITO (indium tin oxide) layer on its surface.
- the pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with smooth surfaces, but also for adherends with uneven surfaces.
- the pressure-sensitive adhesive sheet of the present invention can be used even if at least one of the glass adherend and the resin substrate having a large coefficient of linear expansion has steps on the surface. It is useful for lamination with large resin substrates.
- the adhesive sheet of the present invention is preferably used for manufacturing portable electronic devices.
- portable electronic devices include mobile phones, PHS, smartphones, tablets (tablet computers), mobile computers (mobile PCs), personal digital assistants (PDA), electronic notebooks, portable televisions, portable radios, and the like.
- the pressure-sensitive adhesive sheet of the present invention is preferably used, for example, for attaching members or modules constituting a portable electronic device to each other, fixing members or modules constituting a portable electronic device to a housing, or the like. More specifically, bonding cover glass and lenses (especially glass lenses) with touch panels, touch sensors, and antenna modules, fixing cover glass and lenses (especially glass lenses) to housings, and attaching display panel housings. fixing the antenna module to the housing, fixing input devices such as sheet keyboards and touch panels to the housing, bonding the protective panel of the information display unit to the housing, bonding the housings together, housing Bonding between a body and a decorative sheet, fixing and bonding of various members and modules constituting a mobile electronic device, and the like can be mentioned.
- the display panel refers to a structure composed of at least a lens (particularly a glass lens) and a touch panel.
- the term "lens” used herein is a concept that includes both a transparent body that exhibits light refraction and a transparent body that does not have light refraction.
- a lens in this specification also includes a mere window panel that has no refractive effect.
- the adhesive sheet of the present invention is preferably used for optical applications. That is, the pressure-sensitive adhesive sheet of the present invention is preferably an optical pressure-sensitive adhesive sheet for optical applications. More specifically, for example, it is preferably used for bonding optical members (for bonding optical members) or for manufacturing products (optical products) using the optical member.
- the optical member is an optical member having at least the pressure-sensitive adhesive sheet and a substrate, wherein the substrate has metal electrodes and wiring (e.g., copper, silver, ITO wiring, etc.) on at least one side thereof, and the metal electrodes and wiring of the substrate are
- the pressure-sensitive adhesive layer of the present invention is attached on the side having the
- the pressure-sensitive adhesive sheet may have a separator on the pressure-sensitive adhesive surface until use.
- the optical member preferably has the pressure-sensitive adhesive layer on the side of the substrate opposite to the side having the metal electrodes and wiring, and the surface of the substrate opposite to the side having the metal electrodes and wiring. More preferably, the pressure-sensitive adhesive layer is adhered thereon.
- Examples of materials constituting the metal electrodes and wiring include titanium, silicon, niobium, indium, zinc, tin, gold, silver, copper, aluminum, cobalt, chromium, nickel, lead, iron, palladium, platinum, tungsten,
- Examples include metals such as zirconium, tantalum, and hafnium, and metal oxides such as ITO (oxide of indium and tin), zinc oxide, and tin oxide.
- ITO oxide of indium and tin
- the metal electrodes and wiring are preferably silver, copper or ITO wiring, and particularly preferably ITO wiring. It should be noted that the same applies to the materials constituting the millimeter wave antenna elements described later.
- the metal electrodes and wiring are formed by forming a film of nitride, oxide, sulfide, etc. of the metal for the purpose of hiding the electrodes and / or wiring in order to prevent deterioration of visibility due to reflection of the metal. Blackening treatment may be applied.
- An optical member has optical properties (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, electromagnetic wave permeability, etc.). It means a member that has Examples of the substrate constituting the optical member include a display device (image display device), equipment such as an input device (optical equipment), a substrate constituting an antenna module, or a substrate used in these equipment.
- a display device image display device
- equipment such as an input device (optical equipment)
- a substrate constituting an antenna module or a substrate used in these equipment.
- Polarizing plate wavelength plate, retardation plate, optical compensation film, brightness enhancement film, light guide plate, reflective film, antireflection film, antenna substrate, hard coat film (hard coat treatment applied to at least one side of plastic film such as PET film) film), transparent conductive film (e.g., plastic film having an ITO layer on its surface (preferably ITO film such as PET-ITO, polycarbonate, cycloolefin polymer), etc.), design film, decorative film, surface protection plate, Prisms, lenses, color filters, transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates such as glass plates with transparent electrodes, etc.), and substrates on which these are laminated (these are collectively referred to as may be referred to as a "functional film”) and the like.
- transparent conductive film e.g., plastic film having an ITO layer on its surface (preferably ITO film such as PET-ITO, polycarbonate, cycloolefin polymer), etc.
- design film e.g., decorative film having
- these films may have a metal nanowire layer, a conductive polymer layer, or the like. Further, these films may be mesh-printed with thin metal wires. Moreover, these films may have antenna elements.
- plate and film include forms such as plate-like, film-like, and sheet-like, respectively.
- polarizing film includes “polarizing plate” and “polarizing sheet”. .
- film shall include film sensors and the like.
- the fine metal wire is blackened by forming a film of a nitride, oxide, sulfide, or the like of the metal for the purpose of concealing the deterioration of the visibility due to the reflection of the metal. Also good.
- Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, and the like. Moreover, a touch panel etc. are mentioned as said input device. Further, examples of the antenna module include a millimeter wave antenna, etc., which will be described later.
- substrates constituting the optical member include substrates made of glass, (meth)acrylic resin, polycarbonate, polyethylene terephthalate, cycloolefin polymer, metal thin film, etc. (for example, sheet-shaped, film-shaped, plate-shaped substrates, etc.). etc.
- the "optical member" in the present invention includes members (design films, decorative films, surface protective films, etc.) that play a role of decoration and protection while maintaining the visibility of display devices and input devices. shall be taken.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate and the pressure-sensitive adhesive sheet constitutes a member having optical properties
- the substrate can be regarded as the substrate
- the pressure-sensitive adhesive sheet is the optical member of the present invention. It can be said that it is.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate and the functional film is used as the substrate
- the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer on at least one side of the functional film. It can also be used as an "adhesive functional film”.
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer of the present invention) having a low dielectric constant and dielectric loss in a high frequency band such as millimeter waves, it is possible to suppress the radiation loss of millimeter waves. Therefore, the pressure-sensitive adhesive sheet of the present invention is useful for bonding members constituting an antenna (millimeter wave antenna) used for millimeter wave communication.
- millimeter wave communication means communication in the frequency band of 20 GHz to 300 GHz.
- a substrate (hereinafter referred to as a “millimeter wave antenna substrate”) having an antenna element (hereinafter sometimes referred to as “millimeter wave antenna element”) for transmitting and receiving millimeter waves on at least one side may be called).
- millimeter wave antenna substrate having an antenna element (hereinafter sometimes referred to as “millimeter wave antenna element”) for transmitting and receiving millimeter waves on at least one side may be called).
- millimeter-wave antenna substrate examples include the plastic film used as the base material of the above-mentioned adhesive sheet, and a material with a low dielectric constant and low dielectric loss is preferable in that it can suppress the radiation loss of millimeter waves.
- Cyclic olefin polymers such as "Arton” (manufactured by JSR Corporation) and trade name “Zeonor” (manufactured by Zeon Corporation) are preferred.
- the dielectric constant of the millimeter wave antenna substrate at 28 GHz and/or 60 GHz is preferably 2.0 to 5.0, more preferably 2.1 to 4.5, and still more preferably 2, from the viewpoint of suppressing radiation loss of millimeter waves. .2 to 4.0, more preferably 2.2 to 3.5, more preferably 2.2 to 3.4, more preferably 2.2 to 3.3, more preferably 2.2 to 3.2 , more preferably 2.2 to 3.1, particularly preferably 2.2 to 3.0.
- the dielectric loss of the millimeter wave antenna substrate at 28 GHz and/or 60 GHz is preferably 0.0001 to 0.05, more preferably 0.001 to 0.029, and still more preferably 0.001 to 0.029, from the viewpoint of suppressing the radiation loss of millimeter waves.
- 0.002 to 0.028 is 0.002 to 0.028, more preferably 0.003 to 0.027, more preferably 0.004 to 0.026, more preferably 0.005 to 0.025, more preferably 0.006 to 0 .024, more preferably 0.007 to 0.023, more preferably 0.008 to 0.022, more preferably 0.009 to 0.021, more preferably 0.010 to 0.02, more preferably 0.011 to 0.019, more preferably 0.012 to 0.018, more preferably 0.013 to 0.017, still more preferably 0.014 to 0.016, particularly preferably 0.014 to 0.014 015.
- the millimeter wave antenna substrate is preferably transparent.
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the millimeter wave antenna substrate is preferably 85% or more, more preferably 88% or more, still more preferably 89% or more, and still more preferably 90% or more. , more preferably 91% or more, particularly preferably 92% or more.
- the haze (according to JIS K7136) of the millimeter wave antenna substrate is not particularly limited, but is preferably 1.2% or less, more preferably 1.1% or less, still more preferably 1.0% or less, and still more preferably 1.0% or less. It is 0.9% or less, particularly preferably 0.8% or less.
- the thickness of the millimeter wave antenna substrate is preferably 5 to 250 ⁇ m from the viewpoint of suppressing radiation loss of millimeter waves while mounting the millimeter wave antenna element.
- the millimeter wave antenna substrate may have either a single-layer structure or a multilayer structure.
- the surface of the millimeter wave antenna substrate is appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, chemical treatments such as undercoat treatment, and coating layers such as hard coating. may be used.
- the millimeter wave antenna element provided on the millimeter wave antenna substrate is not particularly limited as long as it can transmit and receive millimeter waves, but a phased array antenna is preferably used from the viewpoint of efficiently receiving millimeter waves with mobile communication devices such as smartphones. can be done.
- a phased array antenna is an antenna that enables transmission and reception in a desired direction by arranging a plurality of antenna elements in an array and controlling the phase of each antenna element.
- a phased array antenna can transmit and receive radio waves in a desired direction by electronically controlling the phase of each antenna element (beam steering) regardless of the direction of the antenna. It becomes possible.
- millimeter wave antenna element known antennas can be used without particular limitation. From antenna structures, slot antenna structures, planar inverted-F antenna structures, monopoles, dipoles, helical antenna structures, Yagi (Yagi-Uda) antenna structures, surface integrated waveguide structures, hybrids of these designs, etc. Antenna elements having resonating elements formed thereon may be mentioned. Different types of mm-wave antenna elements may be used for different frequency band combinations.
- a phased array antenna in which patch antenna elements are arranged in an array is preferable from the viewpoint of efficient reception of millimeter waves by mobile communication devices such as smartphones.
- the material constituting the millimeter wave antenna element is not particularly limited, and examples include titanium, silicon, niobium, indium, zinc, tin, gold, silver, copper, aluminum, cobalt, chromium, nickel, lead, iron, palladium, and platinum. , tungsten, zirconium, tantalum, hafnium, and the like, ITO (indium-tin oxide), zinc oxide, tin oxide, and other metal oxides. Furthermore, materials containing two or more of these metals or metal oxides, and alloys containing these metals as main components are also included. Among them, silver, copper, and ITO are preferred from the viewpoint of conductivity, and ITO is more preferred from the viewpoint of transparency and visibility. That is, it is preferable that the millimeter wave antenna element is made of ITO.
- the antenna element is made of a metal such as silver or copper, a nitride, oxide, sulfide, or the like of the metal is added for the purpose of concealing the antenna element in order to prevent deterioration of visibility due to reflection of the metal.
- a blackening treatment may be performed by forming a film of .
- the millimeter wave antenna substrate may include a transmission line path for transferring signals transmitted and received by the millimeter wave antenna elements to the transmitter/receiver circuit.
- Transmission line paths include coaxial cable paths, microstrip transmission lines, stripline transmission lines, edge-coupled microstrip transmission lines, edge-coupled stripline transmission lines, waveguide structures (e.g. , coplanar waveguides or grounded coplanar waveguides), transmission lines formed from combinations of these types of transmission lines, and the like.
- the material that constitutes the transmission line path is also not particularly limited, and the material that constitutes the millimeter wave antenna element can be used.
- Examples of members that make up the millimeter wave antenna include a cover member laminated on the millimeter wave antenna substrate to protect the millimeter wave antenna elements arranged on the millimeter wave antenna substrate.
- a cover member laminated on the millimeter wave antenna substrate to protect the millimeter wave antenna elements arranged on the millimeter wave antenna substrate.
- optical films such as glass and plastic films can be used.
- plastic films examples include polyester resins such as polyethylene terephthalate (PET); (meth)acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate; triacetyl cellulose (TAC); Polyimide; Transparent polyimide; Polyvinyl chloride; Polyvinyl acetate; Fluorine resin; Polyolefin resin such as polyethylene, polypropylene, ethylene-propylene copolymer; (manufactured by Nippon Zeon Co., Ltd.) and other plastic materials such as cyclic olefin polymers. These plastic materials can be used alone or in combination of two or more.
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- TAC triacetyl cellulose
- Polyimide Transparent polyimide
- Polyvinyl chloride Polyvinyl acetate
- Fluorine resin Polyolefin resin
- Polyethylene, polypropylene, ethylene-propylene copolymer manufactured by Nippo
- the dielectric constant of the cover member at 28 GHz and/or 60 GHz is preferably 2.0 to 5.0, more preferably 2.1 to 4.5, and still more preferably 2.2 in order to suppress radiation loss of millimeter waves. ⁇ 4.0, more preferably 2.2 to 3.5, more preferably 2.2 to 3.4, more preferably 2.2 to 3.3, more preferably 2.2 to 3.2, further It is preferably 2.2 to 3.1, particularly preferably 2.2 to 3.0.
- the dielectric loss of the cover member at 28 GHz and/or 60 GHz is preferably 0.0001 to 0.050, more preferably 0.001 to 0.02, still more preferably 0.001 to 0.02, from the viewpoint of suppressing millimeter wave radiation loss.
- 0.002 to 0.019 more preferably 0.003 to 0.018, more preferably 0.004 to 0.017, still more preferably 0.005 to 0.016, still more preferably 0.006 to 0.016 015, more preferably 0.007 to 0.014, more preferably 0.008 to 0.013, still more preferably 0.009 to 0.012, particularly preferably 0.010 to 0.011.
- the cover member is preferably transparent.
- the total light transmittance of the cover member in the visible light wavelength region is preferably 85% or more, more preferably 88% or more, still more preferably 89% or more, still more preferably 90% or more, and It is preferably 91% or more, particularly preferably 92% or more.
- the haze (according to JIS K7136) of the cover member is preferably 1.2% or less, more preferably 1.1% or less, still more preferably 1.0% or less, still more preferably 0.9% or less, especially Preferably, it is 0.8% or less.
- the thickness of the cover member is preferably 0.025 to 1.5 mm from the viewpoint of suppressing radiation loss of millimeter waves.
- the cover member may have either a single-layer structure or a multilayer structure.
- the surface of the cover member is appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, chemical treatments such as undercoating, and coating layers such as hard coating. good too.
- the adhesive sheet of the present invention is preferably used for manufacturing millimeter wave antennas used in mobile communication devices.
- mobile communication devices include mobile phones, PHS, smart phones, tablets (tablet computers), mobile computers (mobile PCs), and personal digital assistants (PDAs).
- PDAs personal digital assistants
- the millimeter wave antenna may have members other than the millimeter wave antenna substrate, the cover member, and the adhesive sheet described above. , reflective film, anti-reflection film, hard coat film, transparent conductive film, design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, image display panel (e.g. liquid crystal display panel, organic EL panel , plasma display panel, etc.).
- the image display panel may have a touch sensor.
- the millimeter wave antenna may be placed at any position on the mobile communication device, and specifically, may be placed on the front, back, or side of the mobile communication device.
- the front surface of the mobile communication device is the surface that faces the user when the user uses the mobile communication device. do.
- the display panel refers to a structure composed of at least a lens (especially a glass lens) and a touch panel.
- the size (width) of the millimeter wave antenna is not limited either, and it may be formed on the entire surface of each surface of the mobile communication device, or may be arranged on a part thereof.
- the shape of the millimeter wave antenna is not particularly limited, and may be rectangular, circular, or wire-shaped, for example. Alternatively, they may be arranged in a frame shape.
- the number of millimeter wave antennas arranged in the mobile communication device is not limited, either one or a plurality of antennas may be arranged at arbitrary positions. When a plurality of millimeter wave antennas are arranged, the size (width) may be the same or different.
- a dummy pattern without a millimeter wave antenna may be placed in a portion of the mobile communication device where the millimeter wave antenna is not placed in order to improve visibility.
- a millimeter-wave antenna of the present invention is a millimeter-wave antenna comprising at least the adhesive sheet and a substrate, wherein the substrate has an antenna element (millimeter-wave antenna element) on one side, and the substrate (millimeter-wave antenna substrate) of the antenna It is sufficient that the pressure-sensitive adhesive sheet is adhered to the side having the element, and other points are not particularly limited. Since the adhesive sheet in the millimeter wave antenna of the present invention is an adhesive sheet for use, it does not have a separator.
- a millimeter-wave antenna substrate is provided as another optical member (which may or may not necessarily have the above-mentioned adhesive sheet, but having it is more advantageous for millimeter-wave antennas). It is preferable from the point of view of suppressing radiation loss.). Further, the separate optical member may be singular or plural.
- the mode of bonding the millimeter wave antenna of the present invention and the another optical member includes, for example, (1) the millimeter wave antenna substrate of the present invention and the another optical member via the pressure-sensitive adhesive sheet of the present invention; (2) A mode in which the pressure-sensitive adhesive sheet of the present invention, which includes or constitutes a millimeter wave antenna substrate, is bonded to another optical member described above; Examples include a mode in which the antenna substrate is bonded to a member other than the millimeter wave antenna substrate, and (4) a mode in which the adhesive tape of the present invention including or constituting the millimeter wave antenna substrate is bonded to a member other than the millimeter wave antenna substrate.
- the pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet whose substrate is a millimeter wave antenna substrate.
- FIG. 1 shows a millimeter wave antenna having at least a substrate that is an adhesive sheet 10 and a millimeter wave antenna substrate 11.
- the millimeter wave antenna substrate 11 has a millimeter wave antenna element 2 on one side, and the adhesive sheet 10 A millimeter wave antenna 1A attached to the surface of the antenna substrate 11 on the side having the millimeter wave antenna element 2 is shown.
- FIG. 2 shows a millimeter wave antenna 1B having a cover member 12, an adhesive sheet 10, and a millimeter wave antenna substrate 11 in this order in contact with each other.
- the millimeter wave antenna substrate 11 has the millimeter wave antenna element 2 on the surface on the side of the adhesive sheet 10 , and the adhesive sheet 10 is attached to the surface of the millimeter wave antenna substrate 11 on the side having the millimeter wave antenna element 2 .
- the cover member 12 is preferably glass
- the millimeter wave antenna substrate 11 is preferably COP in terms of low dielectric constant and low dielectric loss
- the millimeter wave antenna element 2 is copper, silver, or ITO. is preferred.
- FIG. 3 shows a millimeter wave antenna 1C having a cover member 12, an adhesive sheet 10a, a millimeter wave antenna substrate 11, an adhesive sheet 10b, and an image display panel 13 in this order in contact with each other.
- the millimeter wave antenna substrate 11 has the millimeter wave antenna element 2 on the surface on the side of the adhesive sheet 10a, and the adhesive sheet 10a is adhered to the surface of the millimeter wave antenna substrate 11 on the side having the millimeter wave antenna element 2.
- the cover member 12 is preferably made of glass
- the millimeter wave antenna substrate 11 is preferably made of COP in terms of low dielectric constant and low dielectric loss
- the millimeter wave antenna element 2 is preferably made of COP in terms of transparency and visibility.
- the pressure-sensitive adhesive sheet 10b may be the pressure-sensitive adhesive sheet of the present invention, or may not be the pressure-sensitive adhesive sheet of the present invention, but is preferably the pressure-sensitive adhesive sheet of the present invention.
- the image display panel 13 may have a touch sensor (not shown).
- the adhesive sheets 10, 10a, and preferably the adhesive sheet 10b are composed of the adhesive layer of the present invention with low dielectric constant and dielectric loss in the high frequency band.
- the radiation loss of millimeter waves is suppressed, and millimeter wave communication can be performed efficiently.
- the antenna area can be reduced, and the antenna can be miniaturized.
- Example 1 100 parts by mass of polyisobutylene (trade name “OPPANOL N80”, Mw: 1050000, Mn: 440000, Mw/Mn: 2.4, manufactured by BASF) and fully hydrogenated terpene phenol as a tackifier (softening point: 135 ° C. , a completely hydrogenated terpene phenol having a hydroxyl value of 160) was blended in toluene to prepare a pressure-sensitive adhesive composition (solution) having a solid content of 13% by mass.
- polyisobutylene trade name “OPPANOL N80”, Mw: 1050000, Mn: 440000, Mw/Mn: 2.4, manufactured by BASF
- fully hydrogenated terpene phenol as a tackifier softening point: 135 ° C. , a completely hydrogenated terpene phenol having a hydroxyl value of 160
- the obtained adhesive composition (solution) was applied onto a PET separator (trade name “MRF50”, manufactured by Mitsubishi Chemical Corporation) so that the final thickness (thickness of the adhesive layer) was 75 ⁇ m, A coating layer (adhesive composition layer) was formed. Next, the coating layer was dried at 130° C. for 5 minutes to form an adhesive layer, thereby producing an adhesive sheet having an adhesive layer thickness of 75 ⁇ m.
- a PET separator (trade name “MRF38”, manufactured by Mitsubishi Chemical Corporation) was attached to the adhesive surface of the adhesive sheet so that the release-treated surface and the adhesive layer were in contact with each other. A substrate-less double-sided PSA sheet in which both sides of the PSA layer are protected by separators was obtained.
- Example 2 A mixture of 99 parts by weight of lauryl methacrylate (LMA), 1 part by weight of hydroxyethyl methacrylate (HEMA), and 2,2 as a thermal polymerization initiator are placed in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device. 0.2 parts by mass of '-azobisisobutyronitrile (AIBN) and ethyl acetate as a polymerization solvent are added so that the monomer component becomes 70% by mass, nitrogen gas is flowed, and the mixture is replaced with nitrogen for about 1 hour while stirring. did After that, the reactor was heated to 70° C. and reacted for 6 hours. Further, the reactor was heated to 80° C.
- AIBN '-azobisisobutyronitrile
- AIBN '-azobisisobutyronitrile
- ethyl acetate as a polymerization solvent
- the pressure-sensitive adhesive composition is applied onto a polyethylene terephthalate (PET) separator (trade name “MRF38”, manufactured by Mitsubishi Chemical Corporation) so that the final thickness (thickness of the pressure-sensitive adhesive layer) is 25 ⁇ m.
- PET polyethylene terephthalate
- a layer adheresive composition layer
- drying treatment was performed for 120 minutes in a drier at 130° C. to volatilize residual monomers.
- a PET separator (trade name “MRE38”, manufactured by Mitsubishi Chemical Corporation) is provided on the above coating layer, and consists of only an adhesive layer, and both sides of the adhesive layer are protected by separators. A sticky sheet was obtained.
- Example 3 A substrate-less double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2, except that a monomer mixture composed of 80 parts by mass of lauryl methacrylate (LMA) and 20 parts by mass of hydroxyethyl methacrylate (HEMA) was used.
- LMA lauryl methacrylate
- HEMA hydroxyethyl methacrylate
- Comparative example 1 100 parts by mass of butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 4-hydroxybutyl acrylate (4-HBA) were placed in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device. A monomer mixture was obtained by charging 1 part by mass. Furthermore, with respect to 100 parts by mass of the total monomer mixture, 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator and ethyl acetate as a polymerization solvent are used to make the monomer component 40% by mass. Nitrogen gas was flowed into the flask to replace with nitrogen while gently stirring.
- AIBN 2,2'-azobisisobutyronitrile
- the reactor was heated to 60° C. and reacted for 8 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1,800,000.
- an acrylic polymer solution solid content: 100 parts by mass
- an epoxy-based cross-linking agent trade name "Tetrad C", manufactured by Mitsubishi Gas Chemical Co., Ltd., solid content concentration: 100%
- Parts by mass were added and uniformly mixed to prepare a pressure-sensitive adhesive composition according to this example.
- the pressure-sensitive adhesive composition is applied onto a polyethylene terephthalate (PET) separator (trade name “MRF38”, manufactured by Mitsubishi Chemical Corporation) so that the final thickness (thickness of the pressure-sensitive adhesive layer) is 25 ⁇ m.
- PET polyethylene terephthalate
- a layer adheresive composition layer
- drying treatment was performed for 120 minutes in a drier at 130° C. to volatilize residual monomers.
- a PET separator (trade name “MRE38”, manufactured by Mitsubishi Chemical Corporation) is provided on the above coating layer, and consists of only an adhesive layer, and both sides of the adhesive layer are protected by separators. A sticky sheet was obtained.
- ⁇ Measurement method Open resonator method JIS R1660-2 ⁇ Apparatus: Keycom Co., Ltd., interference type resonator method permittivity measurement system ⁇ Measurement environment: 23 ⁇ 1° C., 52 ⁇ 1% RH
- the size of the millimeter wave patch antenna 43 was adjusted so that it would be optimal when laminated with the adhesives of the respective examples and comparative examples (length A: 2.8 to 3.2 mm, width B: 4.13 mm).
- the adhesive layer 42 of each example/comparative example was attached to the patch antenna 43 side of the antenna film 46 so as to prevent air bubbles and foreign matter from entering. ) to prepare an antenna laminate 4 of cover glass 41 /adhesive layer 42 /antenna film 46 . Feeding from the microstrip line 43a connected to the millimeter-wave patch antenna 43 of various antenna laminates 4, the transmission and reception characteristics in the frequency band of 30 GHz were evaluated. were placed close to each other).
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Abstract
Description
周波数28GHzにおける誘電損失が0.0001~0.05であり、
40℃、92%R.H.における水蒸気透過度(Water Vapor Transmission Rate;WVTR)が430g/m2/day以下であり、
下記式により計算される誘電損失の変化量が0.006以下である、粘着剤組成物を提供する。
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最小値
周波数60GHzにおける誘電損失が0.0001~0.05であり、
40℃、92%R.H.における水蒸気透過度(Water Vapor Transmission Rate;WVTR)が430g/m2/day以下であり、
下記式により計算される誘電損失の変化量が0.003以下である、粘着剤組成物を提供する。
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最小値
本発明の第1の側面の粘着剤組成物は、周波数28GHzにおける誘電率が2.0~5.0であり、周波数28GHzにおける誘電損失が0.0001~0.05であり、40℃、92%R.H.における水蒸気透過度が430g/m2/day以下であり、下記式により計算される誘電損失の変化量が0.006以下である。
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最小値
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最小値
誘電損失の変化量=Dfmax-Dfmin
飽和吸湿率(%)={(w2-w1)/w1}×100
本発明の粘着剤組成物は、混合物、その部分重合物又は共重合体(メタクリル系共重合体)をベースポリマーとするメタクリル系粘着剤組成物であることが好ましい。上記メタクリル系共重合体の含有量は、本発明の粘着剤組成物全量100質量%に対して、特に限定されないが、75質量%以上(例えば75~99.9質量%)であることが好ましく、好ましくは85質量%以上(例えば85~99.9質量%)である。
上記メタクリレート化合物に係る炭素数6以上の炭化水素基は、脂肪族基、脂環含有基又は芳香環含有基を有することが好ましい。これら炭化水素基を有するメタクリレート化合物は、単独で又は2種以上を組み合わせて用いることができる。
上記メタクリル系共重合体は、エステル部に架橋性官能基を有する架橋性官能基含有(メタ)アクリレート化合物を含有するので、架橋剤の使用の場合には架橋されてゲル分率を大きくし、優れた耐発泡剥がれ性を得やすくなる。また、良好な凝集力を得やすくなるので、強接着性を得やすくなる。さらに、高湿環境下で生じる粘着シートの白化を抑制しやすくなる。
上記メタクリル系共重合体は、上記炭素数6以上の炭化水素基を有するメタクリレート化合物、架橋性官能基含有(メタ)アクリレート化合物の他にも、共重合性モノマーを含有していてもよい。共重合性モノマーは、単独で又は2種以上を組み合わせて用いることができる。
カラム:TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
溶媒:テトラヒドロフラン
流速:0.6ml/分
1/Tg=W1/Tg1+W2/Tg2+・・・+Wn/Tgn
・メタクリル酸ラウリル -65℃
・メタクリル酸2-エチルヘキシル -10℃
・アクリル酸ラウリル 0℃
・アクリル酸2-エチルヘキシル -70℃
・メタクリル酸イソデシル -41℃
・メタクリル酸2-ヒドロキシエチル 55℃
・メタクリル酸メチル 105℃
・メタクリル酸シクロヘキシル 66℃
・メタクリル酸イソボルニル 173℃
・メタクリル酸ジシクロペンタニル 175℃
・メタクリル酸 228℃
・N-ビニルピロリドン 86℃
・メタクリル酸2-フェノキシエチル 5℃
・メタクリル酸ベンジル 54℃
・メタクリル酸2-(2-メトキシエトキシ)エチル -3℃
本発明の粘着剤組成物に配合できる無機微粒子としては、例えば、シリカ、アルミナ、ジルコニア、チタニア等の金属酸化物;ホウ酸アルミニウム、水酸化アルミニウム等の金属塩、マイカ等の鉱物、中空ナノシリカ等の中空構造を有する無機微粒子等が挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。
本発明の粘着剤組成物に配合できる有機微粒子としては、例えば、スチレン系樹脂、アクリル系樹脂、シリコーン系樹脂、アクリル-スチレン系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂、アミド系樹脂、ウレタン系樹脂、フェノール系樹脂、スチレン-共役ジエン系樹脂、アクリル-共役ジエン系樹脂、オレフィン系樹脂、フッ素系樹脂等のポリマー、又はこれらポリマーの架橋体により構成された微粒子、さらにはこれらのポリマー・ポリマー架橋体により中空構造を有するよう構成された微粒子等が挙げられる。これららは、単独で又は2種以上を組み合わせて用いることができる。
本発明の粘着剤組成物に配合できるポリマー材料としては、誘電率、誘電損失が低く、ベースポリマーと相溶性を有するものが好ましく、例えば、フッ素樹脂、フッ素ゴム、含フッ素官能基(メタ)アクリレート、ポリエチレン、ポリプロピレン、ポリスチレン、ポリカーボネート、ノルボルネン系樹脂又はオレフィン類との付加共重合型樹脂、ポリフェニレンエーテル、ビスマレイミド・トリアジン・レジン、ポリエーテルイミド、ポリイミド、ポリエーテルエーテルケトン(PEEK)、液晶ポリマー、ゴム・エラストマー、水添ポリオレフィン樹脂、テルペン、イソプレン、テルペンフェノール樹脂、芳香族変性テルペン樹脂及びそれらの水添樹脂等が挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。
本発明の粘着剤組成物は、さらに、防錆剤を含有してもよい。粘着剤組成物に防錆剤が含まれていると、アンテナ素子、金属配線に対する優れた腐食防止効果を得ることができる点で好ましい。
同様の観点から、R2としては、水素原子、モノ又はジC1-10アルキルアミノ-C1-6アルキル基等が好ましく、水素原子、ジC1-8アルキルアミノC1-4アルキル基等がより好ましい。
本発明の粘着剤組成物は、さらに、シランカップリング剤を含有してもよい。粘着剤組成物に、シランカップリング剤が含まれていると、ガラスに対する優れた接着性(特に、高温高湿でのガラスに対する優れた接着信頼性)が得やすくなる点で好ましい。
本発明の粘着剤組成物には、必要に応じて、本発明の特性を損なわない範囲で、酸化防止剤、架橋促進剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、油溶性フェノール等)、老化防止剤、着色剤(顔料や染料等)、紫外線吸収剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤等の公知の添加剤が含まれていてもよい。これらは、単独で又は2種以上を組み合わせて用いることができる。
本発明の粘着剤層は、本発明の粘着剤組成物により形成されているため、高周波数帯(28~60GHz)のミリ波において、低誘電率、低誘電損失を示す。すなわち、本発明の粘着剤層は、ミリ波の放射損失を抑制することができる。
次に、粘着剤層をテトラフルオロエチレンシートで包み凧糸で縛ったもの(「サンプル」と称する)を、酢酸エチルあるいはトルエンで満たした50ml容器に入れ、23℃にて7日間静置する。その後、容器からサンプル(酢酸エチル処理後)を取り出して、アルミニウム製カップに移し、130℃で2時間、乾燥機中で乾燥して酢酸エチルあるいはトルエンを除去した後、質量を測定し、該質量を浸漬後質量(X)とする。
そして、下記の式からゲル分率を算出する。
ゲル分率(%)={(X-Y)/(Z-Y)}×100
誘電損失の変化量=Dfmax-Dfmin
飽和吸湿率(%)={(w2-w1)/w1}×100
本発明の粘着シートは、本発明の粘着剤層を有していれば良く、その他の点では特に限定されない。
本発明の粘着シートは、ミリ波等の高周波数帯における誘電率、誘電損失が低い粘着剤層(本発明の粘着剤層)を有するので、ミリ波の放射損失を抑制することができる。このため、本発明の粘着シートは、ミリ波通信に使用されるアンテナ(ミリ波アンテナ)を構成する部材を貼り合わせる用途に有用である。
ポリイソブチレン(商品名「OPPANOL N80」、Mw:1050000、Mn:440000、Mw/Mn:2.4、BASF社製)100質量部と、粘着付与剤として完全水添テルペンフェノール(軟化点:135℃、水酸基価:160である完全水添テルペンフェノール)22質量部をトルエン中で配合し、固形分が13質量%である粘着剤組成物(溶液)を調製した。得られた粘着剤組成物(溶液)を、PETセパレータ(商品名「MRF50」、三菱ケミカル(株)製)上に最終的な厚み(粘着剤層の厚み)が75μmとなるように塗布し、塗布層(粘着剤組成物層)を形成した。次いで、塗布層を130℃で5分乾燥させて、粘着剤層を形成し、粘着剤層の厚みが75μmの粘着シートを作製した。また、粘着シートの粘着面には、PETセパレータ(商品名「MRF38」、三菱ケミカル(株)製)を、剥離処理面と上記粘着剤層が接するように貼り合せた。粘着剤層の両面がセパレータで保護されている基材レス両面粘着シートを得た。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、メタクリル酸ラウリル(LMA)99質量部、メタクリル酸ヒドロキシエチル(HEMA)1質量部の混合物、熱重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN)0.2質量部、重合溶媒として酢酸エチルをモノマー成分が70質量%になるように投入し、窒素ガスを流し、撹拌しながら約1時間の窒素置換を行った。その後、反応容器を70℃に加熱し、6時間反応させた。更に、反応容器を80℃に加熱し、3時間反応させて重量平均分子量(Mw)40万の(メタ)アクリル系ポリマーを得た。この(メタ)アクリル系ポリマーの溶液(固形分100質量部)に、イソシアネート系架橋剤(商品名「コロネートHX」、東ソー(株)製、固形分濃度100%)を固形分基準で0.1質量部、架橋促進剤としてジオクチルスズジラウレート(商品名「エンビライザーOL-1」、東京ファインケミカル(株)製)0.01質量部、架橋遅延剤としてアセチルアセトン5質量部を加え、均一に混合して、本例に係る粘着剤組成物を調製した。
メタクリル酸ラウリル(LMA)80質量部、メタクリル酸ヒドロキシエチル(HEMA)20質量部から構成されるモノマー混合物を用いたこと以外は、実施例2と同様にして基材レス両面粘着シートを得た。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル(BA)100質量部、アクリル酸(AA)5質量部、アクリル酸4-ヒドロキシブチル(4-HBA)を1質量部仕込むことによってモノマー混合物を得た。さらに、モノマー混合物全体100質量部に対して、熱重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN)0.2質量部、重合溶媒として酢酸エチルをモノマー成分が40質量%になるように投入し、フラスコ内に窒素ガスを流し、緩やかに撹拌しながら窒素置換した。その後、反応容器を60℃に加熱し、8時間反応させて重量平均分子量(Mw)180万のアクリル系ポリマーを得た。このアクリル系ポリマーの溶液(固形分100質量部)に、エポキシ系架橋剤として(商品名「テトラッドC」、三菱ガス化学(株)製、固形分濃度100%)を固形分基準で0.25質量部加え、均一に混合して、本例に係る粘着剤組成物を調製した。
実施例及び比較例の基材レス両面粘着シートについて、下記の測定又は評価を行った。評価結果は表1に示した。
実施例又は比較例で得られた粘着剤層単体(両面粘着シートからシリコーン処理を施したPETセパレータを剥離したもの)を、以下の装置により、周波数28GHz及び60GHzにおける誘電率及び誘電損失を測定した。測定は28GHzの場合は直径8cmの円の領域に対して実施し、60GHzの場合は直径4cmの円の領域に対して実施した。各検体で少なくとも3サンプル作製し、それらの3サンプルの測定値の最大最小の値を除いた後、平均の値を各周波数における誘電率、誘電損失とした。
・測定方法:開放型共振器法 JIS R1660-2
・装置:キーコム(株)製、干渉型共振器法誘電率測定システム
・測定環境:23±1℃、52±1%RH
実施例又は比較例で得られた粘着剤層の水蒸気透過度は、カップ法に基づき評価した。粘着剤層で外部と隔離された塩化カルシウムの乾燥状態の重量(w1)、及び、当該サンプルを40℃、92%R.H.の雰囲気中に放置して所定の時間経過した時点(吸湿率が飽和したとき)の重量(w2)を測定し、重量変化量を単位時間(1日)、単位面積(1m2)に換算することによって水蒸気透過度(g/m2/day)とした。w2の測定は、加湿開始から24時間~48時間経過後の値で算出した。
実施例又は比較例で得られた各粘着剤層単体(両面粘着シートからシリコーン処理を施したPETセパレータを剥離したもの)について、65℃、90%R.H.の雰囲気中において少なくとも5日間以上加湿した。各サンプルについて、23±1℃、52±1%R.H.の条件下に戻し(経過時間=0分)、4分経過してから180分まで10分経過ごとに周波数28GHz及び60GHzにおける誘電率及び誘電損失を、上記の開放型共振器法(JIS R1660-2)に準じて、干渉型共振器法誘電率測定システム(キーコム(株)製)を用いて測定した。各サンプルの誘電損失は、3検体の平均値として得た。
誘電損失の変化量=Dfmax-Dfmin
両面粘着シートから一方のセパレータを剥離して、該両面粘着シートをスライドガラス(松浪硝子工業(株)製、「白研磨 No.1」、厚さ0.8~1.0mm、全光線透過率92%、ヘイズ0.2%)に貼り合わせ、さらに他方のセパレータを剥離して、両面粘着シート(粘着剤層)/スライドガラスの層構成を有する試験片を作製した。上記試験片の可視光領域における全光線透過率及びヘイズを、ヘイズメーター(製品名「HM-150」、(株)村上色彩研究所製)を用いて23±1℃、52±1%RHの環境下において測定した。各検体で3サンプル作製し、それらの3サンプルの測定値の平均を可視光領域における全光線透過率及びヘイズとした。なお、試験片の厚みが大きいほど、全光透過率の値は小さくなり、ヘイズの値は大きくなる。
実施例又は比較例で得られた粘着剤層からサンプルとして10mg採取した。当該サンプルを、加湿機能付きの微量熱重量測定装置(IGA Sorp:型式IG-SA-116、ハイデン社製)に投入し、0.001mgオーダの測定が可能な検出器を用いて、重量変化が観測されなくなるまで130℃で加熱し続けた。次に、同装置内を65℃、0%R.H.の環境下とし、少なくとも1時間保持した後、サンプルの重量変化が観測されなくなった時点(乾燥状態)においてその重量(w1)を測定した。さらに、同装置内を65℃、90%R.H.の雰囲気にし、少なくとも10時間以上、重量変化を追跡した。サンプルの重量変化がなくなった時点(吸湿率が飽和したとき)においてその重量(w2)を測定した。上記結果から、下記式により、飽和吸湿率を求めた。
飽和吸湿率(%)={(w2-w1)/w1}×100
実施例又は比較例で得られた粘着剤層(両面粘着シートからシリコーン処理を施したPETセパレータを剥離したもの)の送受信特性は図4に示される方形マイクロストリップアンテナ(電子通信情報学会4群2編5章「平面アンテナ」、URL:http://www.ieice hbkb.org/files/04/04gun_02hen_05.pdfを参照)により評価した。具体的には、アンテナ基板44として厚み100μmのCOP基材(商品名「ゼオノア」、日本ゼオン(株)製)の表面に図4に示す形状のミリ波用パッチアンテナ43、裏面に1μm厚の銅グラウンド層45が形成された、アンテナフィルム46を作製した。ミリ波用パッチアンテナ43のサイズは、各実施例・比較例の粘着剤と積層した際に最良となるよう調整した(縦A:2.8~3.2mm、横B:4.13mm)。上記アンテナフィルム46のパッチアンテナ43側に各実施例・比較例の粘着剤層42を気泡や異物が入らないように貼り付け、続いてカバーガラス41として厚み0.7mmの化学強化ガラス(コーニング社製)に貼り合わせ、カバーガラス41/粘着剤層42/アンテナフィルム46のアンテナ積層体4を作製した。各種アンテナ積層体4のミリ波用パッチアンテナ43に接続されたマイクロストリップ線路43aより給電し、30GHzの周波数帯における送受信特性を評価し、粘着剤層を用いない場合(カバーガラス41にアンテナフィルム46を近接配置したもの)の利得(5.7dB)より向上したものを〇、低下(悪化)したものを×とした。
10、10a、10b 粘着シート
11 ミリ波アンテナ基板
12 カバー部材
2 ミリ波アンテナ素子
13 画像表示パネル
4 アンテナ積層体
41 カバーガラス
42 粘着剤層
43 ミリ波用パッチアンテナ
43a マイクロストリップ線路
44 アンテナ基板
45 銅グラウンド層
46 アンテナフィルム
Claims (8)
- 周波数28GHzにおける誘電率が2.0~5.0であり、
周波数28GHzにおける誘電損失が0.0001~0.05であり、
40℃、92%R.H.における水蒸気透過度が430g/m2/day以下であり、
下記式により計算される誘電損失の変化量が0.006以下である、粘着剤組成物。
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数28GHzにおける誘電損失が示す最小値 - 周波数60GHzにおける誘電率が2.0~5.0である、請求項1に記載の粘着剤組成物。
- 周波数60GHzにおける誘電率が2.0~5.0であり、
周波数60GHzにおける誘電損失が0.0001~0.05であり、
40℃、92%R.H.における水蒸気透過度が430g/m2/day以下であり、
下記式により計算される誘電損失の変化量が0.003以下である、粘着剤組成物。
誘電損失の変化量=Dfmax-Dfmin
Dfmax:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最大値
Dfmin:65℃、90%R.H.において飽和状態まで加湿した後、23℃±1℃、52±1%R.H.において誘電損失の経時変化を追跡する間に、周波数60GHzにおける誘電損失が示す最小値 - 厚み25μmの粘着剤層について測定した全光透過率が85%以上である、請求項1~3の何れか1項に記載の粘着剤組成物。
- 厚み25μmの粘着剤層について測定したヘイズが1.0%以下である、請求項1~4の何れか1項に記載の粘着剤組成物。
- 請求項1~5の何れか1項に記載の粘着剤組成物により形成される粘着剤層。
- 請求項6に記載の粘着剤層を有する粘着シート。
- 請求項7に記載の粘着シート及び基板を少なくとも有するミリ波アンテナであって、前記基板は少なくとも片面にアンテナ素子を備え、前記基板の前記アンテナ素子を有する側の面上に前記粘着シートが貼着されているミリ波アンテナ。
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WO2022070900A1 (ja) * | 2020-09-29 | 2022-04-07 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、及び粘着シート |
WO2022070899A1 (ja) * | 2020-09-29 | 2022-04-07 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、及び粘着シート |
WO2022070901A1 (ja) * | 2020-09-29 | 2022-04-07 | 日東電工株式会社 | ミリ波アンテナ |
WO2022114097A1 (ja) * | 2020-11-27 | 2022-06-02 | 三菱ケミカル株式会社 | 粘着剤組成物、粘着剤、粘着シートおよび画像表示装置用粘着シート |
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TW202311468A (zh) | 2023-03-16 |
CN117751175A (zh) | 2024-03-22 |
KR20240035575A (ko) | 2024-03-15 |
JP2023016420A (ja) | 2023-02-02 |
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