WO2019078070A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2019078070A1
WO2019078070A1 PCT/JP2018/037824 JP2018037824W WO2019078070A1 WO 2019078070 A1 WO2019078070 A1 WO 2019078070A1 JP 2018037824 W JP2018037824 W JP 2018037824W WO 2019078070 A1 WO2019078070 A1 WO 2019078070A1
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WIPO (PCT)
Prior art keywords
resin layer
laminate
resin
cavity
base material
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PCT/JP2018/037824
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English (en)
French (fr)
Japanese (ja)
Inventor
裕介 塚村
大井　亮
川端　裕介
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2018555792A priority Critical patent/JPWO2019078070A1/ja
Publication of WO2019078070A1 publication Critical patent/WO2019078070A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • 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
    • 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
    • G01N27/416—Systems

Definitions

  • the present invention relates to a laminate, and in particular, examines and determines specific components contained in biological fluids such as blood, urine, saliva, and interstitial fluid, in particular, in various trace amounts of liquid samples.
  • the present invention relates to a laminate suitable for a biosensor used in The laminate of the present invention is provided with a cavity into which the liquid sample is introduced, so that the amount of liquid sample used can be reduced and the manufacturing process can be simplified.
  • Biosensors are used to examine and quantify specific components in various trace amounts of liquid samples, for example, specific components contained in biological fluids such as blood, urine, saliva, and interstitial fluid.
  • biological fluids such as blood, urine, saliva, and interstitial fluid.
  • the reduction of the amount of biological fluid used as a liquid sample is emphasized as one method to reduce the burden on patients when using the sensor. It has been attempted by reducing the volume of the cavity.
  • a configuration is known in which adhesive layers are provided on both surfaces of a spacer substrate, one surface is bonded with a hydrophilic cover, and the other surface is bonded with a substrate on which an electrode is formed (see Patent Document 1). ).
  • the present method not only the thickness of the spacer base material but also the thickness of the adhesive layer formed on both sides increase the volume of the cavity, so that the burden on the patient is large.
  • the present invention is to provide a laminate suitable for a biosensor in which the amount of liquid sample used is reduced and the manufacturing process is simplified.
  • the resin layer X and / or the resin layer Y is made of polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin and acrylic urethane resin
  • the thickness of the spacer is reduced by arranging the resin layer, which has been conventionally arranged as a spacer, as a cover, which is required when introducing the liquid sample. It is possible to reduce the liquid sample. Also, in the conventional configuration shown in FIG. 6, a layer provided with hydrophilicity was provided alone, but by providing hydrophilicity to the resin layer, the layer can simultaneously carry hydrophilicity and adhesiveness. Since integration is possible, the manufacturing process can be simplified. Furthermore, since the present invention is configured to have the resin layer on both sides of the base material A, the contact area of the liquid sample and the resin layer is increased compared to the prior art. Therefore, particularly when the resin layer is hydrophilic, this can improve the introduction speed of the liquid sample.
  • FIG. 1 is a diagram showing the configuration of the laminates 1 and 2 in the first and second embodiments.
  • FIG. 2 is a perspective view of the laminate in FIG.
  • FIG. 3 is a diagram showing a configuration corresponding to the stacks 3 to 18 in Examples 3 to 18.
  • FIG. 4 is a perspective view of the laminate in FIG.
  • FIG. 5 is a conceptual view of a cavity.
  • FIG. 6 is a diagram showing a conventional configuration (a diagram showing the configuration of the stacked body 19 in Comparative Example 1).
  • the present invention relates to a laminate suitable for a biosensor, which is a laminate having a cover material B, a resin layer X, a base material A, a resin layer Y and a cover material C in this order, in the laminate It is a laminate having a cavity provided with an inlet, wherein the cavity is composed of a specific surface.
  • the surface constituting the cavity is constituted only by (i) one surface constituted by the resin layer X, (ii) one surface constituted by the resin layer Y, and (iii) the base material A.
  • the aspect composed of three faces is referred to as Invention 1 and the face constituting the cavity is composed only of (iv) one face composed of the resin layer X, (v) the base material A and the resin layer Y
  • An aspect configured of three faces and (vi) one face composed of the cover material C is referred to as invention 2 and the invention 1 and the invention 2 are collectively referred to as the invention.
  • a biosensor is a device that converts a biological reaction into an electrical signal using an enzyme, a microorganism, or the like.
  • the biosensor has a cavity and has a structure similar to a laminate or a laminate that sucks a liquid sample from the inlet of the cavity, and is used by being inserted into the measuring instrument main body. Because of their shape, biosensors are also sometimes referred to as sensor chips or chips. By combining and using the biosensor and the measuring instrument body, it becomes possible to quantify the substance to be measured contained in the liquid sample introduced into the cavity. The practical use of sensors using enzymes is in progress, and is being developed and used particularly for medical and health management applications.
  • the thickness of the base material A used in the present invention is not particularly limited, but from the viewpoint of improving the assembly workability of the laminate, it is preferable to have flexibility because it is preferable to have 500 ⁇ m or less. From a viewpoint, 10 micrometers or more are preferable. Furthermore, when a plastic film is used as the substrate A, the thickness of the substrate A is preferably 20 ⁇ m to 300 ⁇ m, more preferably 30 ⁇ m to 250 ⁇ m, from the viewpoint of ease of film processing and handling. Moreover, since the thickness of the substrate A is one parameter that defines the volume of the cavity into which the liquid sample is introduced, it is more preferable to be thinner than 200 ⁇ m from the viewpoint of reducing the amount of the liquid sample used.
  • the cavity refers to one provided by completely penetrating at least the base material A in the thickness direction, and is represented by reference numeral 4 in FIGS.
  • the cavity may not only penetrate the base material A in the thickness direction, but also penetrate the resin layer Y in the thickness direction.
  • a cavity penetrating the base material A and the resin layer Y in the thickness direction is represented by reference numeral 4 in FIGS. 3 and 4.
  • the cavity in the present invention as shown in FIG. 5, is provided with an inlet (reference numeral 41) for introducing a liquid sample, and the cavity 4 is composed of a plurality of faces.
  • the cavity 4 has an opening on the inlet side, and a liquid sample can be introduced into the cavity 4 from the inlet.
  • the opposite side of the inlet of a cavity does not become an opening part, but becomes a surface which comprises a cavity.
  • a reagent layer or the like for detecting the composition of 1 and 3 are cross-sectional views of the laminated body cut in the thickness direction between the inlet and the opposite side of the inlet (that is, the surface opposite to the inlet) and viewed from the inlet side. .
  • the base material A has moderate processability in order to form a cavity.
  • a groove provided by scraping the surface of the base material A that is, a groove which does not penetrate the base material A in the thickness direction
  • the method of forming the cavity is not particularly limited, but it is possible to perform physical processing by cutting using scissors or a cutter knife, or by punching using a mold, pinnacle type, Thomson type, engraving type, etc. Alternatively, a known energy beam method represented by laser processing may be used.
  • the cavity may be provided for a configuration in which three layers of the base material A, the resin layer and the silicone resin film described later are laminated, and the cavity may be provided from any surface of the base material A side or the silicone resin film side. It is also good.
  • plastic films synthetic paper, paper or composite sheets subjected to surface treatment are preferable, and among them dimensional stability Plastic films are preferred from the viewpoint of durability and the like.
  • the material of the plastic film is polyester, polyolefin, polyamide, polyesteramide, polyether, polyimide, polyamideimide, polystyrene, polycarbonate, poly-p-phenylene sulfide, polyether ester, polyvinyl chloride, poly (meth) acrylic ester Can be mentioned. Further, these copolymers, blends and further cross-linked compounds can also be used.
  • polyester for example, polyethylene terephthalate, polyethylene 2,6-naphthalate, polyethylene ⁇ , ⁇ -bis (2-chlorophenoxy) ethane 4,4′-dicarboxylate, polybutylene terephthalate, etc.
  • a film is preferable, and among them, a film made of polyethylene terephthalate is particularly preferably used in consideration of mechanical properties, quality such as workability, economy and the like comprehensively.
  • the base material A used in the present invention is preferably a single layer, but for example, a layer having a thickness of 1 ⁇ m or less for the purpose of improving the adhesion strength with the adjacent resin layer X and / or resin layer Y It is good also as a laminated structure which has an easily bonding layer) in surface layer.
  • a layer different from the resin layers X and Y may be provided as necessary. .
  • the electrode layer made of a noble metal such as platinum or palladium may be provided by means of various printing methods such as screen printing or sputtering evaporation method. It is preferable to provide a measurement electrode, a counter electrode, and a detection electrode in the electrode layer provided between the cover material B and the resin layer X adjacent thereto and / or between the cover material C and the resin layer Y adjacent thereto.
  • a reagent layer containing an enzyme that specifically reacts with a specific component in a liquid sample, a mediator, and the like may be formed on the electrode layer.
  • the laminate of the present invention is suitably used as a biosensor. Therefore, a biosensor having the laminate of the present invention has a reagent layer and an electrode layer in addition to the laminate.
  • a method of using a biosensor is shown. After the biosensor with the above configuration is inserted into the measuring instrument body, when blood is brought into contact with the opening of the cavity of the biosensor, blood is drawn into the interior of the cavity and blood is contained in the reagent layer disposed at the tip of the cavity React with the enzyme to generate a current. This current corresponds to the blood glucose level in blood, is transmitted to the measuring instrument body via the mediator and the electrode layer, and is converted to the blood glucose level by the arithmetic device incorporated in the measuring instrument body.
  • the laminate of the present invention is a laminate having the cover material B and the cover material C on each side of the base material A via the resin layers X and Y, and the cover material C and the base material A are cavities. May be configured.
  • the cover film 5 can be comprised by two layers, cover material B21 and resin layer X31, or cover material C22 and resin layer Y32.
  • the laminate 6 of FIG. 1 is a laminate 6 having the cover material B21 and the cover material C22 on the respective surfaces of the base material A1 via the resin layer X31 and the resin layer Y32, and the resin layer X31 together with the base material A1.
  • the resin layer Y 32 constitutes the surface of the cavity 4.
  • the surfaces 7a to 10b of the cavity into which the liquid sample is introduced are preferably hydrophilic.
  • Hydrophilicity is a measure representing the spread of water when water is dropped on the surface.
  • the resin layer for example, the resin layer represented by reference numeral 7a in FIGS. 1 and 3 or 7b in FIG. 1 or 10a or 10b in FIG. High hydrophilicity can be imparted by the following method.
  • “all or a part of at least one surface of the cavity is formed of the resin layer X or the resin layer Y” means, for example, of five surfaces of the cavity as shown by reference numeral 7a in FIG.
  • At least one surface is formed of a resin layer (a mode in which all of at least one surface of the cavity is formed of a resin layer X or a resin layer Y), for example, as shown by reference numerals 10a and 10b in FIG.
  • a resin layer a mode in which all of at least one surface of the cavity is formed of a resin layer X or a resin layer Y
  • reference numerals 10a and 10b in FIG.
  • the cavity in the present invention is provided with the inlet for introducing the liquid sample as described above, and the surface constituting the cavity is (i) one surface constituted of the resin layer X, (ii) the resin layer Y Or (iii) only one surface composed of the resin layer X, (v) only the substrate A and the resin layer Y And (vi) one surface composed of a cover material C.
  • the cavity is composed of a plurality of types of surfaces, adjusting the composition of each surface makes it easy to adjust the hydrophilicity arbitrarily.
  • the surface that constitutes the cavity does not have to be a flat surface. For example, a curved surface that is curved or a surface that has irregularities is also included in the surface that constitutes the cavity.
  • one side composed of the resin layer X in (i) and (iv), as shown by reference numeral 7 a in FIGS. It says to be done.
  • one surface composed of the resin layer Y in (ii) means that one surface constituting the cavity is composed of the resin layer Y, as indicated by reference numeral 7 b in FIG. 1.
  • the “three sides composed only of the base material A” in (iii) means that the three sides constituting the cavity consist only of the base material A, as shown by reference numerals 8a and 8b in FIG. .
  • the surface constituted by the base material A, the resin layer X and the resin layer Y as indicated by reference numerals 12a and 12b in FIG. I assume.
  • the “three faces consisting only of the base material A and the resin layer Y” in (v) means that the three faces constituting the cavity are the base material A and the resin layer Y, as indicated by reference numerals 10a and 10b in FIG. It consists of only.
  • the three surfaces constituting the cavity include the other layer in addition to the base material A and the resin layer Y. Therefore, it shall not correspond to "3 sides comprised only by the base material A and the resin layer Y.”
  • the “one surface made of the cover material C” in (vi) means that one surface of the cavity is made of the cover material C, as indicated by reference numeral 9 in FIG.
  • the cavity processes, for example, the configuration of one layer of the base material A or the configuration in which three layers of the base material A, the resin layer X or the resin layer Y, and a silicone resin film described later are laminated in the vertical direction
  • it has a rectangular parallelepiped shape to provide it.
  • the width of the cavity is preferably such that the liquid sample is introduced stably and rapidly at capillary action.
  • the width of the cavity depends on the surface tension of the liquid sample and the thickness of the substrate A, but is preferably smaller than 50 mm in order to obtain the effect of capillary action.
  • the width of the cavity is preferably larger than 0.1 mm because a width capable of introducing a liquid sample is required.
  • the length of the cavity is not particularly limited, but 3 mm or more and 20 mm or less is preferable. If it is shorter than 3 mm, the variation at the time of inspection may increase. If it is longer than 20 mm, not only the introduction speed of the liquid sample will not be stable, but also the volume may be large, so the amount of liquid sample required may be large.
  • the length in the planar direction of the cavity is not particularly limited, but is preferably 10 mm or less, more preferably 7 mm or less, in order to reduce the amount of liquid sample used.
  • the resin layers X and Y provided on both sides of the substrate A having a cavity are mainly used to bond the surfaces of the two sheets of the substrate A and the cover material B, or the substrate A and the cover material C, respectively.
  • the resin layers X and Y used in the present invention are not limited in composition, curing method, solid content, and the like, but preferably exhibit sufficient adhesive strength to the base material A and the cover material B.
  • the resin layers X and Y provided on both sides of the base material A may be the same or different. That is, the resin layers X and Y provided on both sides of the substrate A may have the same composition, curing method, solid content, etc., or the resin layers X and Y may have different compositions.
  • an adhesive or a hot melt adhesive may be used as the component.
  • the adhesive refers to a coating that adheres an adherend by applying pressure
  • the hot melt adhesive refers to a coating that adheres an adherend by heating.
  • Both adhesives and hot melt adhesives are adhesives that are mainly solid and semi-solid at normal temperature and thermoplastic resin that becomes liquid at high temperature, and are in the form of a solution diluted as a coating liquid with water or an organic solvent. May be
  • main component refers to a component that occupies 80% by mass or more, based on 100% by mass of the entire pressure-sensitive adhesive or hot melt adhesive, and can be the component that most significantly affects the properties of the hot melt adhesive.
  • the hot melt adhesive melts at a low temperature as compared with a thermosetting resin, the heat influence on other members used in the laminate can be suppressed to a small extent.
  • bonding can be performed in a short time, and the workability can be improved.
  • the base material A and the cover material B are disposed via a resin layer (hot melt adhesive), a heat sealer is used, sealing temperature 120 ° C., sealing time 1.0 sec, sealing pressure 0
  • the base material A and the cover material B are adhered under the condition of 2 MPa.
  • the adhesive strength between the base material A and the resin layer Y is evaluated three times according to JIS Z 0237: 2009, peeling speed 50 mm / min, 90 ° peeling, and the average value is 2 It is preferable to show an adhesive strength of not less than 5 N / 10 mm, and more preferable to show an adhesive strength of not less than 5 N / 10 mm.
  • the resin layer X and / or the resin layer Y used in the present invention comprises polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin and acrylic urethane resin It is preferred to contain at least one resin selected from the group. Furthermore, in the case of imparting hydrophilicity to the resin layer X and / or the resin layer Y, it is preferable to contain a surfactant.
  • nonionic surfactant having a polyalkylene glycol skeleton is simply used as a surfactant.
  • an agent sometimes called an agent
  • the hot melt adhesive constituting the laminate it is possible to use a polyester resin or a (meth) acrylic resin as a hot melt adhesive among the above-mentioned groups, as a base material A, a cover material B and a cover material C It is preferable from the viewpoints of adhesive strength of the above and heat resistance. Furthermore, it is particularly preferable to use a polyester resin having a melting point of 40 ° C. or more and 150 ° C. or less or a (meth) acrylic resin as a hot melt adhesive. If the melting point is less than 40 ° C., the hot melt adhesive may flow during heat bonding, and the adhesive may flow to a portion where adhesion is not desired, and may be adhered.
  • the hot melt adhesive preferably has an aromatic skeleton because the cohesion of the resin is improved and the adhesive strength of the resin layer is improved. In addition, only one type of resin described above may be used as the hot melt adhesive, or a plurality of resins may be used.
  • the resin layer X and / or the resin layer Y in the present invention contain a nonionic surfactant having a polyalkylene glycol skeleton together with the above-described hot melt adhesive.
  • the nonionic surfactant having a polyalkylene glycol skeleton used in the present invention has a polyalkylene glycol skeleton as a hydrophilic substituent and a skeleton described later as a hydrophobic substituent.
  • nonionic surfactant having a polyalkylene glycol skeleton for example, polyoxyethylene-alkyl sulfate-sodium salt such as polyoxyethylene lauryl-sulfate sodium salt, polyoxyethylene-lauryl ether, Polyoxyethylene-alkyl ethers such as polyoxyethylene-cetyl ether, polyoxyethylene-oleyl ether, polyoxyethylene-stearyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene-isodecyl ether, etc.
  • polyoxyethylene-alkyl sulfate-sodium salt such as polyoxyethylene lauryl-sulfate sodium salt
  • polyoxyethylene-lauryl ether polyoxyethylene-alkyl ethers such as polyoxyethylene-cetyl ether, polyoxyethylene-oleyl ether, polyoxyethylene-stearyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene-isodecyl ether, etc
  • Polyoxyethylene-alkyl esters such as polyoxyethylene-monolaurate, polyoxyethylene-monostearate, polyoxyethylene-monooleate, polyoxyethylene sorbitan-monolaurate, polyoxyethylene sorbitan-monostearate, polyoxy Sorbitan esters such as ethylene sorbitan-monooleate, polyoxyethylene sorbitan-monooleate, ethylene oxide addition type, Monoglycerides / ethylene oxide addition type such as polyoxyethylene / coco fatty acid glyceryl, Triglycerides / ethylene oxide addition type such as polyoxyethylene-hardened castor oil, Alkylenes such as polyoxyethylene-laurylamine, polyoxyethylene-alkyl (coco) amine, polyoxyethylene-stearylamine, polyoxyethylene-oleylamine, polyoxyethylene-tallow alkylamine, polyoxyethylene alkyl-propylenediamine Polyetheramine-type polyoxyethylene-monomethyl ether, polyoxyethylene-d
  • nonionic surfactants having a polyalkylene glycol backbone compounds having an alkyl substituent as a hydrophobic substituent are more preferable.
  • pionine is a commercially available example of an allylphenyl ether type compound having an arylphenyl group containing an aromatic group as a hydrophobic substituent.
  • the adhesive strength is improved.
  • the hydrophobic substituent is an allylphenyl group
  • sorbitan fatty acid derivatives include Leodol TW-L120, Leodol TW-L106, Leodol TW-P120, and Leodol TW -S120 V, Reodor TW-S106 V, Reodor TW-S-320 V, Reodor TW-O 120 V, Reodor TW-O 106 V, Reodor TW-O 320 V, Reodor TW-IS 399 C, Reodor Super TW-L 120 (all manufactured by Kao Corporation), Pionin D-941, Pionin D-945, Pionin D-945T (all manufactured by Takemoto Yushi Co., Ltd.) and the like can be mentioned.
  • the number average molecular weight (Mn) of the nonionic surfactant having the polyalkylene glycol skeleton constituting the laminate is preferably 500 to 20,000, more preferably 2,000 to 20,000, particularly preferably Is 5,000 to 18,000. That is, when the number average molecular weight is 500 or more, the surfactant component adheres to the transport roll or slit blade surface or cross section during the transport process, the printing process, the slit process or the like when rolling the laminate. Can be well prevented, and as a result, the cleaning frequency of each process is significantly reduced, which is preferable. It is preferable that the number average molecular weight is 20,000 or less, since the surfactant can be easily dispersed uniformly in the resin layer.
  • the melting point or freezing point of the surfactant contained in the resin layer X or the resin layer Y is not particularly limited, but is preferably 30 ° C. or less.
  • the melting point or freezing point is more preferably 25 ° C. or less, still more preferably 20 ° C. or less. If the melting point or the freezing point is higher than 30 ° C., the surfactant is likely to bleed out of the resin layer, and the adhesive strength of the hot melt adhesive may vary, which may result in a decrease in adhesive strength.
  • the amount of surfactant is 0.1 to 100 parts by mass of the resin contained in the resin layer X and the resin layer Y for each of the resin layer X and the resin layer Y.
  • the amount is preferably 20 parts by mass, more preferably 0.1 to 12 parts by mass, and still more preferably 1 to 10 parts by mass. If the amount of surfactant is less than 0.1 parts by mass, the hydrophilicity of the resin layer may not be sufficiently obtained, and the introduction of the liquid sample may not be sufficiently exhibited. Moreover, the effect which prevents that the main component contained in a resin layer adheres in a laminated body conveyance process, a slit process, etc. may not fully be exhibited.
  • the amount of surfactant is more than 20 parts by mass, it is difficult to obtain sufficient compatibility with the hot melt adhesive, and the amount of surfactant which bleeds out on the surface of the resin layer increases, and the adhesiveness of the hot melt adhesive is impaired. The desired adhesive strength may not be obtained. If the amount of the surfactant is larger than 20 parts by mass, the surfactant component may be attached in the laminate conveyance step or the slit step due to bleeding out of the surfactant, which may cause contamination of the processing step.
  • the amount of surfactant is larger than 20 parts by mass, the compounding ratio of the hot melt adhesive is lowered, the strength of the resin layer is lowered, and stable film formation becomes difficult, and the interface with the hot melt adhesive It may cause a decrease in the storage stability of the paint mixed with the activator. It is preferable that the amount of the surfactant is 0.1 to 20 parts by mass because a resin layer in which the above-mentioned disadvantages are solved can be obtained.
  • a hot melt adhesive for example, Aron melt PES-120L, PES-140H, PES-111EE, PES310S30, PES375S40, PPET 1008, PPET 1025, PPET 2102, PPET 1303 S (all manufactured by Toagosei Co., Ltd.), Y-167, H-930 -S, H-180S (above, manufactured by Tanaka Chemical Co., Ltd.), Nichigo Polyester (R) SP-154, SP-165, SP-170, SP-176, SP-180, SP-182, SP-185 ( Above, manufactured by Nippon Synthetic Chemical Co., Ltd.), Byron (R) 200, 240, 300, 550, BX1001 (above, manufactured by Toyobo Co., Ltd.), Polysol (R) SE-1720, SE-4210 E, SE-6210, SE- 6210L (above, Showa Denko shares Company, Ltd.) and the like.
  • the water contact angle of the surface of at least one of the resin layer X and the resin layer Y in the present invention is preferably less than 15 degrees.
  • the contact angle to water being less than 15 degrees is preferable because high-speed and stable introduction of a liquid sample can be sufficiently realized.
  • the water contact angle of the surface of at least one of the resin layer X and the resin layer Y is preferably less than 15 degrees, and the water contact angle of the surfaces of both resin layers is more preferably less than 15 degrees.
  • the surfactant used in the present invention is preferably a surfactant having an HLB value of 8 to 15.
  • the use of a surfactant having an HLB value of 8 to 15 is preferable because hydrophilicity can be imparted to the resin layer while maintaining compatibility with the hot melt adhesive.
  • the HLB (HyDrophile-Lipophile Balance) value is a hydrophilic-lipophilic balance, and is a value calculated by the Griffin method (all revisions new to surfactant introduction p128) obtained from the following formula (1).
  • HLB value of surfactant (number average molecular weight of hydrophilic group portion / number average molecular weight of surfactant) ⁇ 20 Formula (1)
  • HLB value of the surfactant is more than 15, it is difficult to obtain sufficient compatibility between the surfactant and the main component of the resin layer, and the amount of the surfactant which bleeds out on the surface of the resin layer increases and the hot melt adhesive Adhesion may be lost and desired adhesion strength may not be obtained.
  • the HLB value of the surfactant is less than 8 the hydrophilicity of the resin layer may not be sufficiently obtained. It is preferable that the HLB value of the surfactant is 8 to 15, since compatibility with the hot melt adhesive and hydrophilicity of the resin layer can be achieved at the same time.
  • the adhesion amount of the resin layer X and the resin layer Y is preferably 1 to 50 g / m 2 on one side, and more preferably 2 to 30 g / m 2 . If the adhesion amount is less than 1 g / m 2, the adhesion layer may come off, pinholes may occur, or desired adhesion strength may not be obtained due to abrasion during processing. As a result, variations in adhesive strength may occur. When the adhesion amount is more than 50 g / m 2, the effect of preventing the hot melt adhesive component from adhering in the laminate conveyance step, the slit step or the like may be reduced.
  • the resin layer X and the resin layer Y can be formed, for example, by applying a coating solution containing the components constituting the resin layer to the cover material B and the cover material C to form a coating film.
  • a coating solution containing the components constituting the resin layer
  • such a coating liquid can be obtained, for example, by mixing a hot melt adhesive and a surfactant, or by heat-melting it.
  • the coating method of the coating solution is not particularly limited, but methods such as gravure coating, reverse coating, kiss coating, die coating, and bar coating can be used.
  • concentration of the coating solution, the drying condition of the coating film, and the cooling condition of the coating film are not particularly limited, it is desirable that the drying conditions of the coating film be performed in the range which does not adversely affect various characteristics of the substrate.
  • the resin layer X and the resin layer Y of the present invention can also be formed, for example, by previously forming a film-like material with the above-mentioned coating solution and bonding it to the cover material B or the cover material C.
  • bonding for example, a method of applying a coating solution to a release film such as a silicone resin film and transferring it to a cover material is adopted (hereinafter, a two-layer structure of a cover material and a resin layer is a cover film Sometimes called).
  • a two-layer structure of a cover material and a resin layer is a cover film Sometimes called.
  • the base material A having a through hole penetrating in the thickness direction is combined with the resin layer X and the resin layer Y previously formed, and heat treatment is performed, the method of heat treatment is not particularly limited.
  • a press or heat sealer heat sealing roller
  • the laminated body of this invention can be obtained by bonding the cover material B or the cover material C separately prepared also to the back surface of the above-mentioned base material A by heat processing.
  • the coating liquid is formed not on the cover material B or the cover material C but on the base material A
  • a cover film is bonded to the surface on the A side and another cover material is bonded to the resin layer side by heat treatment to obtain a laminate.
  • the contact angle of the resin layer to water is 5 seconds after dropping of pure water (2.0 ⁇ l) onto the surface of the resin layer using DM-400s (manufactured by Kyowa Interface Science Co., Ltd.). The water contact angle of the surface of the resin layer was measured five times, and the average value was taken as the result.
  • the cover material provided with the resin layer and the base material A are evaluated for adhesive strength three times under the conditions of peeling angle 90 ° and peeling speed 50 mm / min according to JIS Z0237: 2009, and the average value As the result.
  • LC / MS / MS is a mass spectrometric technique applicable to non-volatile compounds such as surfactants which are difficult to analyze by LC / MS (gas chromatography mass spectrometer).
  • ⁇ Solution of surfactant contained in resin layer (1) Strip the resin layer from the cover film, and weigh 0.04 g of the resin layer into a 25 mL measuring flask. (2) 1 mL of HFIP (1,1,1,1,3,3,3-hexafluoro-2-propanol) / chloroform (1/1) is added to a volumetric flask to dissolve the resin layer. (3) After adding 2 mL of chloroform, acetonitrile is gradually added to insolubilize the hot melt adhesive component. (4) Add acetonitrile to make the volume 25 mL, and dilute the prepared solution 100 times with acetonitrile. (5) The filtrate obtained by filtering the prepared 100-fold diluted solution with a PTFE disc filter (0.45 ⁇ m) is used as a measurement solution.
  • step (5) The solution obtained in step (5) is subjected to LC / MS / MS, and the retention time and peak area at which the surfactant-derived peak is detected are confirmed from the chromatogram. (7) The formula weight of the surfactant-derived positive ion is confirmed by performing MS analysis on the surfactant-derived peak.
  • Example 1 A 20% by mass solution of a polyester-based adhesive resin having a melting point of 100 ° C. and a number average molecular weight of 22,000 dissolved in toluene is prepared as a resin constituting the hot melt adhesive, and a nonionic surfactant having a polyalkylene glycol skeleton [Kao Co., Ltd. Leodol TW-L106 (HLB value: 13.3)] was prepared, and the coating solution was prepared so that the solid content conversion ratio would be 100 parts by mass / 4 parts by mass.
  • This coating solution is applied to a silicone resin coated surface of a silicone resin film by a comma coater, and dried at 120 ° C.
  • a through hole penetrating in the thickness direction of 10 mm in width by laser processing (a through hole penetrating in the thickness direction of 10 mm in width by laser processing has a shape like the substrate A indicated by reference numeral 1 in FIG.
  • the resin layer side of the cover film 1A is aligned with the Toray Industries Co., Ltd. polyethylene terephthalate (PET) film “Lumirror” (registered trademark) (type 100E20) provided with the part processed in It stuck on the conditions.
  • PET polyethylene terephthalate
  • Limirror registered trademark
  • the 100E 20 side of the obtained sample and the resin layer side of another cover film 1A prepared separately were combined, and laminated again using the heat sealer under the conditions described above, to obtain a laminate 1 of the present invention.
  • the laminate 1 has a configuration corresponding to FIGS. 1 and 2, and the laminate 1 has the configuration of the aspect of the present invention 1.
  • Example 2 In Example 1, prepare a 20% by mass solution in which a polyester adhesive resin having a melting point of 100 ° C. and a number average molecular weight of 22,000 is dissolved in toluene as a resin constituting the hot melt adhesive in one piece of the resin layer 1a.
  • the laminated body 2 of the present invention was obtained in the same manner except that the resin layer 2b obtained in the above was used.
  • the laminate 2 has a configuration corresponding to FIGS. 1 and 2, and the laminate 2 has the configuration of the aspect of the present invention 1.
  • Example 3 A resin layer 2b is provided on a silicone resin film, and a polyethylene terephthalate (PET) film "Lumirror” (registered trademark) (type 100E20) manufactured by Toray Industries, Inc. is bonded to the surface of the resin layer 2b, and a punching method using a Thomson type And a through hole penetrating in the thickness direction of 10 mm in width. Then, the spacer film 3 was obtained by peeling a silicone type resin film. After bonding the resin layer 2b surface of the obtained spacer film 3 to a polyethylene terephthalate (PET) film "Lumirror” (registered trademark) (type 100S28) manufactured by Toray Industries, Inc.
  • PET polyethylene terephthalate
  • a laminate 3 of the present invention was obtained by bonding the surface of the cover film 1A separately prepared, and the spacer base of the spacer film 3, using a heat sealer under the conditions of Example 1.
  • the laminate 3 has a configuration corresponding to FIGS. 3 and 4, and the laminate 3 has the configuration of the embodiment of the present invention 2.
  • Example 4 In Example 3, using a magnetron sputtering apparatus on the bonding surface side of Toray Industries, Ltd. polyethylene terephthalate (PET) film "Lumirror” (registered trademark) (type 188E20), a palladium layer with a thickness of 10 nm was used as a film base A laminate 4 of the present invention was obtained in the same manner except that the cover material 4 formed on one surface was provided on the resin layer 2b surface of the spacer film 3.
  • PET polyethylene terephthalate
  • Limirror registered trademark
  • the laminate 4 has a configuration corresponding to FIGS. 3 and 4, and the laminate 4 has the configuration of the aspect of the present invention 2.
  • Example 5 a nonionic surfactant having a polyalkylene glycol skeleton [Leodor TW-L106 (HLB value: 13.3) manufactured by Kao Corp.) is a ratio of the solid content conversion ratio of the hot melt adhesive of 8 parts by mass.
  • a laminate 5 of the present invention was obtained in the same manner except that the coating liquid was prepared as described above.
  • the laminate 5 has a configuration corresponding to FIGS. 3 and 4, and the laminate 5 has the configuration of the aspect of the present invention 2.
  • Example 6 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1508 (HLB value: 11.4) manufactured by Takemoto Yushi Co., Ltd.] in a proportion of 4 parts by mass in terms of solid content conversion of hot melt adhesive
  • the laminate 6 of the present invention was obtained in the same manner as described above except that the coating liquid was prepared.
  • the laminate 6 has a configuration corresponding to FIGS. 3 and 4, and the laminate 6 has the configuration of the embodiment of the present invention 2.
  • Example 7 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1508 (HLB value: 11.4), manufactured by Takemoto Yushi Co., Ltd.] was added to a proportion of 3 parts by mass of the solid content of the hot melt adhesive.
  • the laminate 7 of the present invention was obtained in the same manner except that the coating liquid was prepared to be
  • the laminate 7 has a configuration corresponding to FIGS. 3 and 4, and the laminate 7 has the configuration of the aspect of the present invention 2.
  • Example 8 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1508 (HLB value: 11.4) manufactured by Takemoto Yushi Co., Ltd.] in a proportion of 20 parts by mass in terms of the solid content conversion of the hot melt adhesive
  • the laminate 8 of the present invention was obtained in the same manner except that the coating liquid was prepared to be
  • the laminate 8 has a configuration corresponding to FIGS. 3 and 4, and the laminate 8 has the configuration of the aspect of the present invention 2.
  • Example 9 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1105-S (HLB value: 10.5) manufactured by Takemoto Oil & Fats Co., Ltd.] was converted to a solid content ratio of 4 parts by mass of the hot melt adhesive.
  • a laminate 9 of the present invention was obtained in the same manner except that the coating liquid was prepared to have a ratio.
  • the laminate 9 has a configuration corresponding to FIGS. 3 and 4, and the laminate 9 has the configuration of the aspect of the present invention 2.
  • Example 10 (Example 10)
  • a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1105-S (HLB value: 10.5) manufactured by Takemoto Oil & Fats Co., Ltd.] was converted to a solid content ratio of 8 parts by mass of the hot melt adhesive.
  • a laminate 10 of the present invention was obtained in the same manner except that the coating liquid was prepared to have a ratio.
  • the laminate 10 has a configuration corresponding to FIGS. 3 and 4, and the laminate 10 has the configuration of the aspect of the second invention.
  • Example 11 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton (Emulgen 103 (HLB value: 8.1) manufactured by Kao Corp.) is made to have a ratio of 4 parts by mass of the solid content conversion ratio of the hot melt adhesive A laminate 11 of the present invention was obtained in the same manner except that the coating solution was prepared.
  • the laminate 11 has a configuration corresponding to FIGS. 3 and 4, and the laminate 11 has the configuration of the aspect of the present invention 2.
  • Example 12 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Emulgen 103 (HLB value: 8.1) manufactured by Kao Corp.] is made to have a ratio of the solid content conversion ratio of the hot melt adhesive of 8 parts by mass.
  • a laminate 12 of the present invention was obtained in the same manner except that a coating solution was prepared.
  • the laminate 12 has a configuration corresponding to FIGS. 3 and 4, and the laminate 12 has the configuration of the aspect of the present invention 2.
  • Example 13 In Example 4, the proportion of the nonionic surfactant having a polyalkylene glycol skeleton [Nucargen D-1205 (HLB value: 10.5) manufactured by Takemoto Yushi Co., Ltd.] to the solid content conversion ratio of the hot melt adhesive is 4 parts by mass
  • the laminate 13 of the present invention was obtained in the same manner except that the coating liquid was prepared to become
  • the laminate 13 has a configuration corresponding to FIGS. 3 and 4, and the laminate 13 has the configuration of the aspect of the present invention 2.
  • Example 14 In Example 4, the ratio of the solid content conversion ratio of the hot melt adhesive to 8 parts by mass of a nonionic surfactant having a polyalkylene glycol skeleton [Nucargen D-1205 (HLB value: 10.5) manufactured by Takemoto Yushi Co., Ltd.]
  • the laminate 14 of the present invention was obtained in the same manner except that the coating liquid was prepared to be
  • the laminate 14 has a configuration corresponding to FIGS. 3 and 4, and the laminate 14 has the configuration of the aspect of the present invention 2.
  • Example 15 In Example 4, the nonionic surfactant having a polyalkylene glycol skeleton [DTD-51 (HLB value: 13.7), manufactured by Takemoto Yushi Co., Ltd.] is a ratio of 4 parts by mass of the solid content conversion ratio of the hot melt adhesive
  • DTD-51 HLB value: 13.7
  • Example 16 In Example 4, the nonionic surfactant having a polyalkylene glycol skeleton [DTD-51 (HLB value: 13.7) manufactured by Takemoto Oil & Fats Co., Ltd.] is a ratio of the solid content conversion ratio of the hot melt adhesive of 8 parts by mass.
  • a laminate 16 of the present invention was obtained in the same manner except that the coating liquid was prepared as described above.
  • the laminate 16 has a configuration corresponding to FIGS. 3 and 4, and the laminate 16 has the configuration of the aspect of the second invention.
  • Example 17 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1007 (HLB value: 14.1), manufactured by Takemoto Yushi Co., Ltd.] in a proportion of 4 parts by mass of the solid content conversion ratio of the hot melt adhesive
  • the laminate 17 of the present invention was obtained in the same manner except that the coating solution was prepared to be
  • the laminate 17 has a configuration corresponding to FIGS. 3 and 4, and the laminate 17 has the configuration of the aspect of the second invention.
  • Example 18 In Example 4, a nonionic surfactant having a polyalkylene glycol skeleton [Pionin D-1007 (HLB value: 14.1), manufactured by Takemoto Oil & Fats Co., Ltd.] in a ratio of 8 parts by mass in terms of solid content conversion of hot melt adhesive
  • the laminate 18 of the present invention was obtained in the same manner except that the coating liquid was prepared to be
  • the laminate 18 has a configuration corresponding to FIGS. 3 and 4, and the laminate 18 has the configuration of the aspect of the present invention 2.
  • a hot melt resin layer was provided on the silicone resin coated surface of the silicone resin film by the same procedure, and the hot melt resin layer was transferred to the other surface of the previous 100E20. Furthermore, the spacer film 19B was obtained by providing the through-hole penetrated in the thickness direction. Next, a palladium layer was formed on one side of a polyethylene terephthalate (PET) film "Lumirror” (registered trademark) (type 188E20) manufactured by Toray Industries, Inc. using a magnetron sputtering apparatus. The hydrophilic coated surface of the cover film 19A and the hot melt resin layer surface of the spacer film 19B were bonded using a heat sealer under the conditions described above.
  • PET polyethylene terephthalate
  • the laminated body 19 is a structure which has the hydrophilic-coat layer 11 corresponding to FIG. 6, and does not have the structure of the laminated body prescribed
  • FIG. FIG. 6 is a cross-sectional view of the laminate cut in the thickness direction between the inlet and the opposite side of the inlet (that is, the surface opposite to the inlet) and viewed from the inlet side.

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PCT/JP2018/037824 2017-10-20 2018-10-10 積層体 WO2019078070A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12129102B1 (en) * 2024-01-23 2024-10-29 Dongguan Taihong Packaging Co., Ltd High-strength packaging bag with effects of heat preservation and watertightness, and preparation process thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006030160A (ja) * 2004-04-14 2006-02-02 Hitachi Maxell Ltd 反応容器
JP2011185744A (ja) * 2010-03-09 2011-09-22 Toray Ind Inc バイオセンサに用いられるカバーフィルム
WO2011125750A1 (ja) * 2010-03-31 2011-10-13 シーシーアイ株式会社 バイオセンサ
JP2014215193A (ja) * 2013-04-26 2014-11-17 東洋インキＳｃホールディングス株式会社 液体分析部材用粘着シートおよび液体分析部材
JP2015182334A (ja) * 2014-03-25 2015-10-22 東レ株式会社 金属ドット基板およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006030160A (ja) * 2004-04-14 2006-02-02 Hitachi Maxell Ltd 反応容器
JP2011185744A (ja) * 2010-03-09 2011-09-22 Toray Ind Inc バイオセンサに用いられるカバーフィルム
WO2011125750A1 (ja) * 2010-03-31 2011-10-13 シーシーアイ株式会社 バイオセンサ
JP2014215193A (ja) * 2013-04-26 2014-11-17 東洋インキＳｃホールディングス株式会社 液体分析部材用粘着シートおよび液体分析部材
JP2015182334A (ja) * 2014-03-25 2015-10-22 東レ株式会社 金属ドット基板およびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12129102B1 (en) * 2024-01-23 2024-10-29 Dongguan Taihong Packaging Co., Ltd High-strength packaging bag with effects of heat preservation and watertightness, and preparation process thereof

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