WO2015146503A1 - 無機薄膜積層フィルム - Google Patents

無機薄膜積層フィルム Download PDF

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WO2015146503A1
WO2015146503A1 PCT/JP2015/056141 JP2015056141W WO2015146503A1 WO 2015146503 A1 WO2015146503 A1 WO 2015146503A1 JP 2015056141 W JP2015056141 W JP 2015056141W WO 2015146503 A1 WO2015146503 A1 WO 2015146503A1
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film
thin film
inorganic thin
nickel
inorganic
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PCT/JP2015/056141
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English (en)
French (fr)
Japanese (ja)
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宗範 河本
阿部　和洋
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東洋紡株式会社
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Priority to JP2015515058A priority Critical patent/JP6197869B2/ja
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/307—Disposable laminated or multilayered electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry

Definitions

  • the present invention relates to an inorganic thin film laminated film, and since it is excellent in laser processability, it relates to an inorganic thin film laminated film suitably used for an electrode film for a blood glucose level sensor.
  • the blood glucose level sensor is used by a diabetic patient or a person suspected of having diabetes to measure a blood glucose level several times a day and manage the numerical value.
  • a patterned electrode film in which thin films of noble metals such as gold and platinum are laminated is used.
  • laser processing is disclosed for patterning an electrode film (see Patent Document 1).
  • an object of the present invention is to provide an electrode film for a biosensor such as a blood glucose level sensor, which is an inexpensive inorganic thin film, has excellent laser processability and has a low surface resistance, in view of the above-described conventional problems. It is providing the inorganic thin film laminated film which can be used conveniently as.
  • this invention consists of the following structures.
  • An inorganic thin film laminated film in which an inorganic thin film is laminated directly on at least one surface of a film substrate or via another layer, and the outermost inorganic thin film is nickel, nickel-copper alloy, nickel-palladium alloy, indium
  • An inorganic thin film laminated film comprising any one of tin oxides, wherein the film substrate has a total light transmittance of 50% or less.
  • the inorganic thin film laminated film according to the first aspect wherein the reflectance of the film substrate is 50% or more.
  • the outermost inorganic thin film is a nickel-copper alloy having an inorganic intermediate layer between the film substrate and the nickel-copper alloy thin film, and the inorganic intermediate layer is a thin film of either titanium or nickel-titanium alloy.
  • the inorganic thin film laminated film according to the first or second aspect which is characterized in that it exists. 4).
  • the outermost inorganic thin film is any one of nickel, nickel-palladium alloy, and indium tin oxide, and has an inorganic intermediate layer between the film base and the outermost thin film, and the inorganic intermediate layer is nickel-
  • the inorganic thin film laminated film according to the first or second aspect which is a thin film selected from a copper alloy, titanium and a nickel-titanium alloy. 5.
  • the inorganic thin film laminated film according to the third or fourth aspect wherein the total thickness of the outermost inorganic thin film and the inorganic intermediate layer is 5 nm or more and 400 nm or less. 6).
  • An electrode film for a blood glucose level sensor wherein the inorganic thin film laminated film according to any one of the first to fifth aspects is subjected to laser patterning. 7).
  • a blood glucose sensor strip comprising the electrode film for a blood glucose sensor according to the sixth aspect. 8).
  • a blood glucose level sensor device comprising the blood glucose level sensor strip according to the seventh aspect.
  • an inorganic thin film laminated film that is an inexpensive inorganic thin film, has excellent laser processability, has a low surface resistance, and can be suitably used as an electrode film for a biosensor such as a blood glucose level sensor. Made possible.
  • the inorganic thin film laminated film in the present invention is an inorganic thin film laminated film obtained by laminating an inorganic thin film directly on at least one surface of a film base or via another layer, and the total light transmittance of the film base is 50. % Or less, more preferably 45% or less. When it is larger than 50%, it becomes difficult to improve the laser processability.
  • the total light transmittance is preferably small, and may be zero.
  • the surface resistance value of the inorganic thin film laminated film in the present invention is preferably 300 ⁇ / ⁇ or less, more preferably 250 ⁇ / ⁇ or less, and particularly preferably 200 ⁇ / ⁇ or less.
  • the surface resistance value is preferably low, but usually 0 ⁇ / ⁇ is not usually achieved, and the lower limit may be 0.01 ⁇ / ⁇ , or 1 ⁇ / ⁇ or more.
  • the inorganic thin film laminated film of the present invention has a structure in which an inorganic thin film is laminated directly on at least one surface of a film substrate or via another layer.
  • it is a structure in which an inorganic thin film is laminated directly on one side of a film substrate or via another layer, and is an inorganic thin film laminated film that is sufficiently suitable for use as an electrode film for a blood glucose level sensor.
  • each layer will be described in detail.
  • the film substrate used in the present invention is formed by forming an organic polymer into a film by melt extrusion or solution extrusion into a film, and stretching, heat setting, heat relaxation in the longitudinal direction and / or the width direction as necessary. It is a film that has been treated.
  • Organic polymers include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamideimide, polyethersulfane, polyetheretherketone , Polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polystyrene, syndiotactic polystyrene, norbornene-based polymer, and the like.
  • organic polymers polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, syndiotactic polystyrene, norbornene polymer, polycarbonate, polyarylate and the like are preferable. These organic polymers may be copolymerized with a small amount of other organic polymer monomers, or may be blended with other organic polymers.
  • the thickness of the film substrate used in the present invention is preferably 10 to 300 ⁇ m, more preferably 20 to 250 ⁇ m. If the thickness of the plastic film is 10 ⁇ m or more, it is preferable because the mechanical strength can be satisfied and the handling of a sensor such as a blood glucose level sensor can be secured. On the other hand, a thickness of 300 ⁇ m or less is preferable because the thickness of a sensor such as a blood glucose level sensor does not become too thick.
  • the film substrate used in the present invention is a film having a total light transmittance of 50% or less, and a white film can be preferably used as such a film substrate.
  • a white film can be preferably used as such a film substrate.
  • a cavity-containing film substrate having a cavity ratio of 3 to 50% by volume can be suitably used as a film substrate having a total light transmittance of 50% or less.
  • the total light transmittance smaller than 3% may not be 50% or less, which is not preferable.
  • it is larger than 50% sufficient strength as a substrate may not be secured, which is not preferable.
  • a thermoplastic resin that is incompatible with the organic polymer (thermoplastic resin) constituting the base film is mixed, melt-extruded, cooled and solidified, and then stretched at least in a uniaxial direction.
  • thermoplastic resin incompatible with the polyester examples include polyethylene, polypropylene, polymethylpentene, and the like.
  • Polyolefin, polystyrene, cyclic polyolefin, polyacryl, polycarbonate, polysulfone, cellulose resin and the like can be employed.
  • the film base material containing white fillers such as a titanium oxide, barium sulfate, a calcium carbonate, a silica, an alumina, an organic particle
  • the film base material containing a titanium oxide with a high refractive index and barium sulfate can be used conveniently.
  • the content of the white filler is preferably in the range of 0.2 to 50% by weight.
  • the total light transmittance smaller than 0.2% by weight may not be 50% or less, which is not preferable.
  • the content of the white filler is larger than 50% by weight, it may be difficult to secure sufficient strength as a substrate, which is not preferable.
  • the base film if the total light transmittance is 50% or less, a laminate of a cavity-containing layer and a white filler-containing layer can be suitably used.
  • the void-containing layer may be located outside or inside.
  • a single layer may contain both cavities and white fillers.
  • a cavity-containing layer and a layer that does not contain a cavity may be laminated.
  • the cavity-containing layer is an A layer and a layer that does not contain a cavity is a B layer
  • the A layer / B layer, B layer / A layer / B layer, B layer / A layer / other C layer laminated structures can be employed, and the film substrate having these laminated structures with a total light transmittance of 50% or less is composed of B layer and C layer. This is preferable in that the surface is smooth.
  • the white filler may be contained in the A layer, in the B layer, or in both the A layer and the B layer.
  • the layer thickness ratio of the A layer: B layer is preferably 2: 1 or more from the viewpoint of reducing the total light transmittance due to the inclusion of cavities, and more preferably 4: 1 or more.
  • the layer thickness ratio of the A layer: B layer is preferably 20: 1 or less. In the case of a configuration in which a plurality of B layers are present in the film substrate, the calculation is made based on the layer thickness of the B layer.
  • the film substrate used in the present invention is a surface such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc. on the above-mentioned film within the range not impairing the object of the present invention.
  • An activation treatment may be performed.
  • the film substrate used in the present invention is a cured product comprising a curable resin as a main component for the purpose of improving adhesion to an inorganic thin film, imparting chemical resistance, and preventing precipitation of low molecular weight substances such as oligomers. It is also preferred to provide a layer.
  • the curable resin is not particularly limited as long as it is a resin that is cured by application of energy such as heating, ultraviolet irradiation, electron beam irradiation, etc., and silicone resin, acrylic resin, methacrylic resin, epoxy resin, melamine resin, polyester resin, urethane Resin etc. are mentioned.
  • energy such as heating, ultraviolet irradiation, electron beam irradiation, etc.
  • silicone resin acrylic resin, methacrylic resin, epoxy resin, melamine resin, polyester resin, urethane Resin etc.
  • the inorganic thin film in the present invention is preferably a thin film made of nickel, a nickel-copper alloy, a nickel-palladium alloy, or indium tin oxide, and may be a laminate in which these are laminated.
  • the nickel content is preferably 40% by weight or more and the copper content is preferably 60% by weight or less. Outside this range, the electrode may be eluted in the sensor test, and the blood glucose level It is difficult to use as an electrode for a sensor and is not so preferable.
  • the nickel content may be 100% by weight, but it is more preferable that the nickel-copper alloy has a nickel content of 95% by weight or less and a copper content of 5% or more.
  • the productivity of lamination by sputtering may decrease, which is not so preferable.
  • the weight ratio of indium is preferably 40 to 100% by weight, and the weight ratio of tin is preferably 60 to 0% by weight, and substantially 100% by weight of indium.
  • indium is 97% by weight or less and tin is 3% by weight or more.
  • Nickel-palladium alloy can be suitably used in any composition.
  • nickel-copper alloy nickel-copper alloy, nickel-palladium alloy, or indium tin oxide, titanium
  • nickel-copper is placed between the film substrate
  • a thin film layer of an alloy when the inorganic thin film is a nickel-copper alloy, two thin films of the same material
  • a nickel-titanium alloy may be provided as the inorganic intermediate layer.
  • Nickel-copper alloy and nickel-titanium alloy as the inorganic intermediate layer can be suitably used in any composition, but copper in the nickel-copper alloy and titanium in the nickel-titanium alloy are present in an amount of 3% by weight or more. From the viewpoint of easiness of film formation, it is preferable.
  • the total film thickness of the inorganic thin film and the inorganic intermediate layer is preferably in the range of 5 to 400 nm, more preferably 10 to 300 nm, and particularly preferably 15 to 200 nm.
  • this film thickness is less than 5 nm, a thin film pinhole is generated, which makes it difficult to obtain an electrical signal when used as an electrode of a blood glucose level sensor, which is not preferable.
  • this film thickness is thicker than 400 nm, the stress of the inorganic thin film is increased, peeling is likely to occur, adhesion may be reduced, and warping of the substrate may also occur. It is not preferable.
  • a vacuum deposition method As a method for forming an inorganic thin film in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and the above method is appropriately selected according to a required film thickness.
  • the sputtering method is preferable from the viewpoint of developing high adhesion and reducing variations in film thickness.
  • means such as plasma irradiation and ion assist may be used in combination.
  • a bias such as direct current, alternating current, and high frequency may be applied to the substrate as long as the object of the present invention is not impaired.
  • the pressure in the vacuum chamber is evacuated to a vacuum degree of 0.0005 Pa or less (attainment vacuum degree is 0.0005 Pa or less) before sputtering, and then Ar or the like is not discharged. It is preferable to perform sputtering by introducing an active gas into a vacuum chamber, generating discharge in a pressure range of 0.01 to 10 Pa.
  • the DC sputtering method is preferable from the viewpoint of productivity, and the DC magnetron sputtering method is more preferable. The same applies to other methods such as vapor deposition and CVD.
  • an inorganic thin film is formed on a film by a vacuum process such as sputtering.
  • a vacuum process such as sputtering.
  • the performance of the inorganic thin film laminated film may be adversely affected, which is not preferable.
  • the plastic film contains a volatile component
  • the sputtered inorganic particles collide with gas volatilized from the plastic film in the gas phase.
  • the energy of the inorganic particles decreases.
  • the adhesiveness of the inorganic thin film formed on the plastic film tends to decrease, which is not preferable.
  • the volatile components present in the plastic film include low molecular weight components such as moisture and oligomers absorbed in the film.
  • the heat treatment temperature at this time is preferably in the range of 0 to 200 ° C. If it is less than 0 ° C., the effect of reducing the volatile components tends to be insufficient, which is not preferable, and if it exceeds 200 ° C., it is difficult to maintain the flatness of the film, which is not preferable.
  • the reason which can be implemented by heating at 0 ° C. or more as the lower limit is that the vacuum may be performed in a substantially vacuum state.
  • the pressure at this time is preferably 1000 Pa or less, and more preferably 100 Pa or less.
  • the pressure is higher than 1000 Pa, the effect of removing volatile components tends to be insufficient, which is not preferable.
  • the pressure is preferably low, and the lower limit is 1 ⁇ 10 ⁇ 6 Pa.
  • the vacuum exposure time is preferably 1 to 100 minutes. If the vacuum exposure time is less than 1 minute, the effect of removing volatile components tends to be insufficient, which is not preferable. On the other hand, when the time exceeds 100 minutes, productivity is lowered, which is not preferable industrially.
  • the film temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 180 ° C.
  • the roll set temperature at this time is preferably in the range of 0 to 200 ° C., more preferably in the range of 20 to 180 ° C., similarly to the film temperature.
  • the infrared heater may be any of a near infrared type, a middle infrared type, and a far infrared type.
  • the input power to the infrared heater is preferably in the range of 5 to 50000 W / m 2 ⁇ min. An input power of less than 5 W ⁇ m 2 / min is not preferable because the effect of increasing the film temperature is poor, and an input power higher than 50000 W / m 2 ⁇ min is not preferable, and the film temperature becomes too high and the flatness of the film is deteriorated. This is not preferable.
  • an electrode film having an inorganic thin film excellent in adhesion to the substrate and film quality can be obtained by removing impurities such as moisture and organic matter in the film forming atmosphere as much as possible. Therefore, when this electrode film is used for a blood glucose level sensor, the reliability of the sensor is not impaired.
  • the inorganic thin film laminated film obtained as described above is patterned by a laser and is preferably used as an electrode film for a blood glucose level sensor.
  • the electrode film for a blood glucose level sensor is formed on a blood glucose level sensor strip corresponding to the type of the blood glucose level sensor device, and is used by being attached to the blood glucose level sensor device.
  • Yb YAG laser processing
  • Yb YAG laser (YLP-1-100-20-20) manufactured by IPG was used.
  • the laser wavelength is 1060 nm
  • the pulse width is 100 ns
  • the frequency is 20 kHz.
  • an irradiation spot diameter of 30 ⁇ m an inorganic thin film (with the outermost inorganic thin film and the intermediate layer removed if there is an intermediate layer) with a line of 0.5 mm in width and 20 mm in length with the number of irradiations per dot / one dot.
  • the laser was irradiated with varying laser power so that it could be removed.
  • a strip having a width of 10 mm was cut out in a direction perpendicular to the irradiated line, and the electrical resistance between the two points was measured in such a manner as to straddle the irradiated part.
  • the minimum laser output at which the resistance value could not be measured was P1 (W).
  • the minimum laser output at which the resistance value could not be measured was defined as P2 (W).
  • CO 2 laser processing A CO 2 laser (VersaLaser) manufactured by Laser Works was used. With a spot diameter of 72 ⁇ m, with an irradiation speed of 1270 mm / second, an inorganic thin film (with the outermost inorganic thin film and the intermediate layer removed if there is an intermediate layer) with a line of 0.5 mm width and 20 mm length The laser was irradiated with varying laser power so that it could be removed. A strip having a width of 10 mm was cut out in a direction perpendicular to the irradiated line, and the electrical resistance between the two points was measured in such a manner as to straddle the irradiated part.
  • the minimum laser output at which the resistance value could not be measured was P3 (W).
  • the minimum laser output at which the resistance value could not be measured was defined as P4 (W).
  • Total light transmittance of film base material Based on JIS-K7136, total light transmittance of the film base material was measured using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.
  • the inorganic thin film is dissolved with concentrated sulfuric acid, concentrated nitric acid or concentrated hydrochloric acid. Measure after.
  • the inorganic thin film on the inorganic thin film laminated film can oxidize ferrocyanide ions to ferricyanide ions without dissolving them in ferrocyanide ions, and it does not dissolve in ferricyanide ions. It is confirmed that it can be reduced to ferrocyanide ion, and it is confirmed that it can withstand repeated use as an electrode film for blood glucose level sensors.
  • Example 1 Biaxially stretched as a plastic film with a thickness of 250 ⁇ m containing rutile-type titanium oxide with an average particle size of 0.45 ⁇ m at 10% by weight, a total light transmittance of 1.8%, and a reflectance of 96.3%. A polyester film was used.
  • the film was subjected to vacuum exposure.
  • the rewinding process was performed in a vacuum chamber, the pressure at this time was 2 ⁇ 10 ⁇ 3 Pa, and the exposure time was 20 minutes.
  • the set temperature of the center roll was 40 ° C.
  • a nickel thin film was formed on one side of the biaxially stretched polyester film using a nickel target.
  • sputtering was performed after confirming that the ultimate pressure of the vacuum chamber before sputtering was 1 ⁇ 10 ⁇ 4 Pa (degree of ultimate vacuum).
  • DC power of 3 W / ⁇ was applied.
  • Ar gas was flowed, it was made into the atmosphere of 0.4 Pa, and it formed into a film using DC magnetron sputtering method.
  • the center roll set temperature was 0 ° C.
  • a nickel thin film having a thickness of 100 nm was deposited.
  • FIG. 1 shows a cyclic voltammogram of the cyclic voltammetry measurement results of the nickel thin film laminated film. An oxidation peak current was observed at a potential between +0.2 V and +0.5 V, and a reduction peak current was observed at a potential between 0 V and +0.3 V. Further, it was confirmed that the first measurement and the second measurement were substantially the same, and the electrode film for a blood glucose level sensor could withstand repeated use.
  • Example 1 The same procedure as in Example 1 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 2 The same operation as in Example 1 was performed except that a titanium thin film having a thickness of 50 nm was laminated and a nickel thin film having a thickness of 50 nm was further laminated thereon. Compared to the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 2 below, it is recognized that the laser output at which the resistance value cannot be measured is lowered. It was.
  • Example 2 The same procedure as in Example 2 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 3 On one side of a biaxially stretched polyester film containing 20% by weight of barium sulfate having an average particle size of 0.3 ⁇ m at 20% by weight and having a reflectance of 96.1%, nickel (65 nm The same procedure as in Example 1 was performed except that an alloy thin film of (wt%)-palladium (35 wt%) was formed. Compared to the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 3 below, it is recognized that the laser output at which the resistance value cannot be measured is lowered. It was.
  • Example 3 The same procedure as in Example 3 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 4 On one side of a biaxially stretched polyester film containing 20% by weight of barium sulfate having an average particle size of 0.3 ⁇ m at 20% by weight and having a reflectance of 96.1%, nickel (75 nm The same procedure as in Example 1 was performed except that an alloy thin film of (wt%)-palladium (25 wt%) was formed. Compared to the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 4 below, it is recognized that the laser output at which the resistance value cannot be measured is lowered. It was.
  • Example 4 The same operation as in Example 4 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 5 On one side of a biaxially stretched polyester film containing 20% by weight of barium sulfate having an average particle size of 0.3 ⁇ m at 20% by weight and having a reflectance of 96.1%, nickel (5 nm Weight%)-titanium (50% by weight) alloy thin film and a 50 nm-thick nickel (75% by weight) -palladium (25% by weight) alloy thin film was further formed thereon. It carried out similarly. Compared to the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 5 below, it is recognized that the laser output at which the resistance value cannot be measured is lowered. It was.
  • Example 5 The same procedure as in Example 5 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 6 The same procedure as in Example 6 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 7 The same procedure as in Example 7 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • the same procedure as in Example 1 was performed except that the layers were further laminated and further subjected to a heat treatment at 150 ° C. for 1 hour.
  • a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 8 below, it is recognized that the laser output at which the resistance value cannot be measured is lowered. It was.
  • Example 8 The same procedure as in Example 8 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 9 On one side of a biaxially stretched polyethylene terephthalate having a thickness of 250 ⁇ m and a total light transmittance of 44.4% and a reflectivity of 51.3% containing 2% by weight of rutile titanium oxide having an average particle size of 0.45 ⁇ m.
  • Example 1 was performed except that an alloy thin film of nickel (65 wt%)-copper (35 wt%) was formed. Compared to the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 9 below, it is recognized that the laser output at which the resistance value cannot be measured is reduced. It was.
  • Example 9 The same procedure as in Example 9 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 10 A titanium thin film with a thickness of 50 nm is formed on one side of a biaxially stretched polyester film containing 20% by weight of barium sulfate having an average particle size of 0.3 ⁇ m and having a total light transmittance of 1.9% and a reflectance of 96.1%.
  • the same procedure as in Example 1 was performed except that a nickel (75 wt%)-copper (25 wt%) alloy thin film having a thickness of 100 nm was further laminated thereon.
  • a nickel (75 wt%)-copper (25 wt%) alloy thin film having a thickness of 100 nm was further laminated thereon.
  • a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 10 below, it is recognized that the laser output at which the resistance value cannot be measured decreases. It was.
  • Example 10 The same procedure as in Example 10 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 11 On one side of a biaxially stretched polyester film containing 7.0% barium sulfate having an average particle size of 0.3 ⁇ m at 10% by weight and having a reflectance of 86.1%, nickel (50 nm) (% By weight) -titanium (50% by weight) alloy thin film was laminated, and a nickel (90% by weight) -copper (10% by weight) alloy thin film having a thickness of 100 nm was further laminated thereon. Performed as in Example 1. In comparison with the case where a film having a total light transmittance of 88% and a reflectance of 4.5% is used as a base material in Comparative Example 11 below, it is recognized that the laser output at which the resistance value cannot be measured decreases. It was.
  • Example 11 The same procedure as in Example 11 was performed except that the base film was changed to a biaxially stretched polyester film having a total light transmittance of 88% and a reflectance of 4.5%.
  • Example 12 On one side of a cavity-containing biaxially stretched polyester film having a total light transmittance of 2.1% and a reflectance of 95.7% (formed by mixing 80% by weight of polyethylene terephthalate and 20% by weight of polystyrene) This was carried out in the same manner as in Example 1 except that a titanium thin film having a thickness of 50 nm was laminated, and further an alloy thin film of nickel (75% by weight) -copper (25% by weight) having a thickness of 100 nm was laminated thereon. . As compared with the case where the film having the total light transmittance of 88% in Comparative Example 10 was used as the base material, it was recognized that the laser output at which the resistance value could not be measured was lowered.
  • Example 13 A layer is made of polyethylene terephthalate containing 5% by weight of rutile type titanium oxide having an average particle size of 0.45 ⁇ m and 15% by weight of polystyrene, and B layer is made of polyethylene terephthalate.
  • the film thickness is 50 nm on one side of a cavity-containing biaxially stretched polyester film having a total thickness of 250 ⁇ m and a total light transmittance of 2.0%, a reflectance of 96.0%, and a layer thickness ratio of 1/8/1. This was carried out in the same manner as in Example 1 except that a titanium (100%) nickel (75% by weight) -copper (25% by weight) alloy thin film was further laminated thereon.
  • the void-containing biaxially stretched polyester film substrate had a smooth surface and was preferable compared to the void-containing biaxially stretched polyester film substrate of Example 12.
  • the thin film laminated films of Examples 2 to 13 were also confirmed and evaluated by cyclic voltammetry measurement, and it was confirmed that they could withstand repeated use as a blood glucose sensor electrode film.
  • a laser that can ensure insulation is better when a film substrate with a total light transmittance of 50% or less is used than when a film substrate with a total light transmittance of more than 50% is used. It can be confirmed that the output decreases. That is, according to the present invention, easy and efficient laser processing can be achieved.
  • the present invention although it is an inexpensive inorganic thin film laminated film, it can provide an inorganic thin film laminated film having excellent laser processability and low surface resistance and chemical resistance. It can be suitably used as an electrode film.

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  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
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WO2017112688A1 (en) * 2015-12-23 2017-06-29 Materion Corporation Nickel alloys for biosensors

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TWI803996B (zh) * 2021-10-06 2023-06-01 立寶光電股份有限公司 檢測試片及電極製造方法

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JPS63303730A (ja) * 1987-06-05 1988-12-12 Sumitomo Bakelite Co Ltd 金属薄膜蒸着ポリエ−テルイミドフィルム
JPH0955575A (ja) * 1995-08-10 1997-02-25 Mitsui Toatsu Chem Inc 積層体
JP2010126807A (ja) * 2008-12-01 2010-06-10 Hitachi Cable Ltd 表面処理金属材およびその製造方法

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KR20050085331A (ko) * 2002-12-05 2005-08-29 가부시키가이샤 가네카 적층체, 인쇄 배선판 및 이들의 제조 방법
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JPS63303730A (ja) * 1987-06-05 1988-12-12 Sumitomo Bakelite Co Ltd 金属薄膜蒸着ポリエ−テルイミドフィルム
JPH0955575A (ja) * 1995-08-10 1997-02-25 Mitsui Toatsu Chem Inc 積層体
JP2010126807A (ja) * 2008-12-01 2010-06-10 Hitachi Cable Ltd 表面処理金属材およびその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017112688A1 (en) * 2015-12-23 2017-06-29 Materion Corporation Nickel alloys for biosensors
US10808273B2 (en) 2015-12-23 2020-10-20 Materion Corporation Nickel alloys for biosensors
US11299761B2 (en) 2015-12-23 2022-04-12 Materion Corporation Nickel alloys for biosensors

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