WO2019078070A1 - Laminate - Google Patents
Laminate Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin layer
- laminate
- resin
- cavity
- base material
- Prior art date
Links
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Images
Classifications
-
- 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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Abstract
In view of this prior art background, the present invention provides a laminate that is suitable for a biosensor which reduces the amount of use of a liquid sample, while having a simplified production process. A laminate which sequentially comprises a cover material B, a resin layer X, a base material A, a resin layer Y and a cover material C in this order, and which is characterized in that: the laminate internally has a cavity that is provided with a feed port; and the cavity is configured from a specific surface.
Description
本発明は、積層体に関するものであり、特に種々の微量の液体試料中の特定成分、例えば血液、尿、唾液や細胞間質液等といった、生体液中に含まれる特定の成分を検査・定量する際に用いられるバイオセンサに好適な積層体に関するものである。本発明の積層体は液体試料が導入されるキャビティを具備することで、液体試料の使用量を低減できると共に、製造工程の簡略化を可能にすることができるものである。
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.
種々の微量の液体試料中の特定成分、例えば血液、尿、唾液や細胞間質液等といった生体液中に含まれる特定の成分を検査・定量する際にバイオセンサが用いられる。様々な構成のバイオセンサが提案されているが、いずれの構成にも液体試料が導入されるキャビティが具備されている。このキャビティは、一般にスペーサとカバーと呼ばれる二つの部材から成り、スペーサに用いられる基材A(以下、スペーサ基材と記載することもある)とカバー材料Bあるいはカバー材料C(以下、カバー材料Bあるいはカバー材料Cそれぞれについて、または両者を総称してカバー材料と記載することもある。)が樹脂層を介して貼り合わせされることによって形成されるものもある。
バイオセンサにおいて、液体試料として用いる血液、尿、唾液や細胞間質液等といった生体液の使用量の削減は、センサ使用時の患者への負担を減らす一つの手法として重視されており、従来からキャビティの容積を減らすことで図られてきた。
例えば、スペーサ基材の両面に接着層を設け、一方の面を親水性のカバーで、もう一方の面を電極の形成された基材で貼り合せた構成が知られている(特許文献1参照)。しかしながら、本手法ではスペーサ基材の厚みのみならず、その両面に形成された接着層の厚みもキャビティの体積を増加させてしまうため、患者への負担が大きい状態であった。 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. Although various configurations of biosensors have been proposed, any configuration has a cavity into which a liquid sample is introduced. This cavity consists of two members generally called a spacer and a cover, and a base material A (hereinafter sometimes referred to as a spacer base material) used for the spacer and a cover material B or a cover material C (hereinafter, cover material B) Alternatively, each of the cover materials C or both may be collectively referred to as a cover material.) May be formed by bonding through a resin layer.
In biosensors, the reduction of the amount of biological fluid used as a liquid sample, such as blood, urine, saliva, and interstitial fluid, 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.
For example, 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). ). However, in 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.
バイオセンサにおいて、液体試料として用いる血液、尿、唾液や細胞間質液等といった生体液の使用量の削減は、センサ使用時の患者への負担を減らす一つの手法として重視されており、従来からキャビティの容積を減らすことで図られてきた。
例えば、スペーサ基材の両面に接着層を設け、一方の面を親水性のカバーで、もう一方の面を電極の形成された基材で貼り合せた構成が知られている(特許文献1参照)。しかしながら、本手法ではスペーサ基材の厚みのみならず、その両面に形成された接着層の厚みもキャビティの体積を増加させてしまうため、患者への負担が大きい状態であった。 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. Although various configurations of biosensors have been proposed, any configuration has a cavity into which a liquid sample is introduced. This cavity consists of two members generally called a spacer and a cover, and a base material A (hereinafter sometimes referred to as a spacer base material) used for the spacer and a cover material B or a cover material C (hereinafter, cover material B) Alternatively, each of the cover materials C or both may be collectively referred to as a cover material.) May be formed by bonding through a resin layer.
In biosensors, the reduction of the amount of biological fluid used as a liquid sample, such as blood, urine, saliva, and interstitial fluid, 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.
For example, 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). ). However, in 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.
本発明は、かかる従来技術の背景に鑑み、液体試料の使用量を低減すると共に、製造工程が簡略化されたバイオセンサに好適な積層体を提供することにある。
SUMMARY OF THE INVENTION In view of the background of the prior art, 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.
本発明は、かかる課題を解決するために、次のような手段を採用するものである。
(1)カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(i)の面、(ii)の面および(iii)の面から構成されることを特徴とする積層体。
(i)樹脂層Xで構成される1面
(ii)樹脂層Yで構成される1面
(iii)基材Aのみで構成される3面
(2)カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(iv)の面、(v)の面および(vi)の面から構成されることを特徴とする積層体。
(iv)樹脂層Xで構成される1面
(v)基材Aおよび樹脂層Yのみで構成される3面
(vi)カバー材料Cで構成される1面
(3)前記樹脂層Xまたは樹脂層Yの少なくとも一方の樹脂層の表面の水接触角が15度未満である(1)または(2)に記載の積層体。
(4)前記基材Aと樹脂層YとのJIS Z0237:2009に準拠した引きはがし角度90°の接着強度が、2.5N/10mm以上である(1)~(3)のいずれかに記載の積層体。
(5)前記樹脂層Xおよび/または樹脂層Yに界面活性剤を含有する(1)~(4)のいずれかに記載の積層体。
(6)前記樹脂層Xおよび/または樹脂層Yが、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1つの樹脂を含有する(1)~(5)のいずれかに記載の積層体。
(7)前記界面活性剤がポリアルキレングリコール骨格を有する非イオン性の界面活性剤である(5)または(6)に記載の積層体。 The present invention adopts the following means in order to solve the problems.
(1) 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, which has a cavity having an inlet in the laminate, and the cavity is A laminate comprising the following (i) surface, (ii) surface and (iii) surface.
(I) One surface composed of resin layer X (1) One surface composed of resin layer Y (iii) Three surfaces composed only of base material A (2) Cover material B, resin layer X, base material A, a laminate having a resin layer Y and a cover material C in this order, which has a cavity having an inlet in the laminate, and the cavity has the following surface (iv), the surface of (v) And a laminate comprising the surface of (vi).
(Iv) One surface composed of resin layer X (3) Three surfaces composed only of base material A and resin layer Y (vi) One surface composed of cover material C (3) The resin layer X or resin The laminated body as described in (1) or (2) whose water contact angle of the surface of the at least one resin layer of layer Y is less than 15 degrees.
(4) The adhesive strength according to JIS Z 0237: 2009 between the base material A and the resin layer Y according to any one of (1) to (3), wherein the adhesive strength at a peel angle of 90 ° is 2.5 N / 10 mm or more. Stacks.
(5) The laminate according to any one of (1) to (4), wherein a surfactant is contained in the resin layer X and / or the resin layer Y.
(6) A group in which 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 laminate according to any one of (1) to (5), which contains at least one resin selected from the group consisting of
(7) The laminate according to (5) or (6), wherein the surfactant is a nonionic surfactant having a polyalkylene glycol skeleton.
(1)カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(i)の面、(ii)の面および(iii)の面から構成されることを特徴とする積層体。
(i)樹脂層Xで構成される1面
(ii)樹脂層Yで構成される1面
(iii)基材Aのみで構成される3面
(2)カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(iv)の面、(v)の面および(vi)の面から構成されることを特徴とする積層体。
(iv)樹脂層Xで構成される1面
(v)基材Aおよび樹脂層Yのみで構成される3面
(vi)カバー材料Cで構成される1面
(3)前記樹脂層Xまたは樹脂層Yの少なくとも一方の樹脂層の表面の水接触角が15度未満である(1)または(2)に記載の積層体。
(4)前記基材Aと樹脂層YとのJIS Z0237:2009に準拠した引きはがし角度90°の接着強度が、2.5N/10mm以上である(1)~(3)のいずれかに記載の積層体。
(5)前記樹脂層Xおよび/または樹脂層Yに界面活性剤を含有する(1)~(4)のいずれかに記載の積層体。
(6)前記樹脂層Xおよび/または樹脂層Yが、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1つの樹脂を含有する(1)~(5)のいずれかに記載の積層体。
(7)前記界面活性剤がポリアルキレングリコール骨格を有する非イオン性の界面活性剤である(5)または(6)に記載の積層体。 The present invention adopts the following means in order to solve the problems.
(1) 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, which has a cavity having an inlet in the laminate, and the cavity is A laminate comprising the following (i) surface, (ii) surface and (iii) surface.
(I) One surface composed of resin layer X (1) One surface composed of resin layer Y (iii) Three surfaces composed only of base material A (2) Cover material B, resin layer X, base material A, a laminate having a resin layer Y and a cover material C in this order, which has a cavity having an inlet in the laminate, and the cavity has the following surface (iv), the surface of (v) And a laminate comprising the surface of (vi).
(Iv) One surface composed of resin layer X (3) Three surfaces composed only of base material A and resin layer Y (vi) One surface composed of cover material C (3) The resin layer X or resin The laminated body as described in (1) or (2) whose water contact angle of the surface of the at least one resin layer of layer Y is less than 15 degrees.
(4) The adhesive strength according to JIS Z 0237: 2009 between the base material A and the resin layer Y according to any one of (1) to (3), wherein the adhesive strength at a peel angle of 90 ° is 2.5 N / 10 mm or more. Stacks.
(5) The laminate according to any one of (1) to (4), wherein a surfactant is contained in the resin layer X and / or the resin layer Y.
(6) A group in which 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 laminate according to any one of (1) to (5), which contains at least one resin selected from the group consisting of
(7) The laminate according to (5) or (6), wherein the surfactant is a nonionic surfactant having a polyalkylene glycol skeleton.
本発明によれば、かかる従来技術の背景に鑑み、従来スペーサとして配されていた樹脂層がカバーとして配されることでスペーサ厚みが低減され、これにより液体試料を導入する際に必要とされる液体試料の低減が可能となる。また、図6に示す従来の構成では親水性を付与した層を単独で設けていたが、親水性を樹脂層に付与することで、該層が親水性と接着性を同時に担う一つの層に統合できるため、製造工程の簡略化を図ることができる。
さらに、本発明は基材Aの両面に樹脂層を有する構成であるため、液体試料と樹脂層の接触する面積が従来よりも増加する。そのため、特に樹脂層が親水性である場合には、これによって液体試料の導入速度の向上を図ることができる。 According to the present invention, in view of the background of the prior art, 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.
さらに、本発明は基材Aの両面に樹脂層を有する構成であるため、液体試料と樹脂層の接触する面積が従来よりも増加する。そのため、特に樹脂層が親水性である場合には、これによって液体試料の導入速度の向上を図ることができる。 According to the present invention, in view of the background of the prior art, 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.
以下に、本発明について、好ましい実施の形態とともに詳細に説明する。本発明は、バイオセンサに好適な積層体に関するものであり、カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが特定の面から構成されることを特徴とする積層体である。
The present invention will be described in detail below along with preferred embodiments. 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.
また本発明において、キャビティを構成する面が、(i)樹脂層Xで構成される1面、(ii)樹脂層Yで構成される1面、および(iii)基材Aのみで構成される3面から構成される態様を、本発明1といい、キャビティを構成する面が、(iv)樹脂層Xで構成される1面、(v)基材Aおよび樹脂層Yのみで構成される3面、および(vi)カバー材料Cで構成される1面から構成される態様を、本発明2といい、本発明1と本発明2を総称して、本発明という。
バイオセンサとは、酵素や微生物等を利用して生体反応を電気信号に変換するものである。また、バイオセンサは、キャビティを有し、キャビティの導入口から液体試料を吸引する積層体あるいは積層体に類する構成をとり、測定器本体に挿入して使用される。その形状から、バイオセンサは一般に、センサチップあるいはチップと称される場合もある。バイオセンサと測定器本体を組み合わせて使用することで、キャビティに導入された液体試料中に含まれる測定対象物質の定量が可能となる。酵素を利用したセンサの実用化が進んでおり、特に医療や健康管理用途で開発や利用がされている。 In the present invention, 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 asInvention 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. In addition, 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.
バイオセンサとは、酵素や微生物等を利用して生体反応を電気信号に変換するものである。また、バイオセンサは、キャビティを有し、キャビティの導入口から液体試料を吸引する積層体あるいは積層体に類する構成をとり、測定器本体に挿入して使用される。その形状から、バイオセンサは一般に、センサチップあるいはチップと称される場合もある。バイオセンサと測定器本体を組み合わせて使用することで、キャビティに導入された液体試料中に含まれる測定対象物質の定量が可能となる。酵素を利用したセンサの実用化が進んでおり、特に医療や健康管理用途で開発や利用がされている。 In the present invention, 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
A biosensor is a device that converts a biological reaction into an electrical signal using an enzyme, a microorganism, or the like. In addition, 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.
本発明に用いる基材Aの厚みは、特に限定はないが、積層体の組立て作業性を向上させる観点から、フレキシブル性を有する方が好ましいため500μm以下が好ましく、引張りや衝撃に対する強度を確保する観点から、10μm以上が好ましい。さらに、基材Aとしてプラスチックフィルムを用いる場合、基材Aの厚みは、フィルムの加工やハンドリングの容易性から、20μm~300μmが好ましく、より好ましくは30μm~250μmである。また、基材Aの厚みは、液体試料を導入するキャビティの容積を規定する一つのパラメータであるため、液体試料の使用量を低減する観点から、200μmより薄いことがさらに好ましい。
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 μm 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 μm to 300 μm, more preferably 30 μm to 250 μm, 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 μm from the viewpoint of reducing the amount of the liquid sample used.
キャビティは、少なくとも基材Aを厚み方向に完全に貫通することで設けられたものをいい、図1~4の符号4で表される。また、キャビティは、基材Aを厚み方向に貫通するのみならず、樹脂層Yを厚み方向に貫通していてもよい。例えば、基材Aおよび樹脂層Yを厚み方向に貫通したキャビティは、図3および図4の符号4で表される。本発明におけるキャビティは、図5に示すように、液体試料を導入するための導入口(符号41)を備えており、さらにキャビティ4は複数の面から構成されるものである。該キャビティ4は、図2、4および5に示すように、導入口側が開口部となっており、該導入口から液体試料をキャビティ4内に導入することができる。また、キャビティの導入口の反対側は開口部となっておらず、キャビティを構成する面となっている。この結果、導入口から導入された液体試料が導入口の反対側から溢れ出ることを防ぐことができるとともに、さらにキャビティの先端(キャビティの奥部、つまりキャビティの導入口から遠い位置)に液体試料の組成を検出するための試薬層などを設けることができる。なお、図1、3は導入口と該導入口の反対側(すなわち、該導入口に対向する面)との間で積層体を厚み方向に切断し、導入口側から見た断面図である。
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. For example, 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. As shown in FIGS. 2, 4 and 5, the cavity 4 has an opening on the inlet side, and a liquid sample can be introduced into the cavity 4 from the inlet. Moreover, the opposite side of the inlet of a cavity does not become an opening part, but becomes a surface which comprises a cavity. As a result, it is possible to prevent the liquid sample introduced from the introduction port from overflowing from the opposite side of the introduction port, and further, to the liquid sample at the tip of the cavity (the far end of the cavity, that is, the position far from the introduction port of the 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. .
また基材Aは、キャビティを形成するために、適度な加工性を有することが好ましい。なお、例えば基材Aの表面を削り取ることで設けた溝(すなわち、基材Aを厚み方向に貫通していない溝)は、キャビティに含まない。キャビティを形成する方法は、特に限定されないが、ハサミやカッターナイフを用いた切り取り、あるいは金型、ピナクル型、トムソン型、彫刻型などを用いた打ち抜きの手法にて物理的な加工を行ってもよいし、レーザー加工に代表される公知のエネルギー線を用いる方法を用いてもよい。キャビティは、基材A、樹脂層および後述するシリコーン系樹脂フィルムの3層が積層された構成に対し設けてもよく、キャビティを基材A側またはシリコーン系樹脂フィルム側の何れの面から設けてもよい。
Moreover, it is preferable that the base material A has moderate processability in order to form a cavity. In addition, for example, 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) is not included in the cavity. 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.
本発明で用いられる基材A、カバー材料B、カバー材料Cの形態には特に制限はないが、例えばプラスチックフィルム、合成紙、紙または表面処理が施された複合シートが好ましく、中でも寸法安定性や耐久性等の点からプラスチックフィルムが好ましい。
プラスチックフィルムの材質としては、ポリエステル、ポリオレフィン、ポリアミド、ポリエステルアミド、ポリエーテル、ポリイミド、ポリアミドイミド、ポリスチレン、ポリカーボネート、ポリ-ρ-フェニレンスルフィド、ポリエーテルエステル、ポリ塩化ビニル、ポリ(メタ)アクリル酸エステルが挙げられる。また、これらの共重合体やブレンド物やさらに架橋した化合物を用いることもできる。
さらに、上記プラスチックフィルムの中でも、ポリエステル、例えば、ポリエチレンテレフタレート、ポリエチレン2,6-ナフタレート、ポリエチレンα,β-ビス(2-クロルフェノキシ)エタン4,4’-ジカルボキシレート、ポリブチレンテレフタレートなどからなるフィルムが好ましく、これらの中で機械的特性、作業性などの品質、経済性などを総合的に勘案すると、ポリエチレンテレフタレートからなるフィルムが特に好ましく用いられる。 There are no particular limitations on the form of the substrate A, cover material B, and cover material C used in the present invention, but for example, 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.
Furthermore, among the above-mentioned plastic films, polyester, for example, polyethylene terephthalate,polyethylene 2,6-naphthalate, polyethylene α, β-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.
プラスチックフィルムの材質としては、ポリエステル、ポリオレフィン、ポリアミド、ポリエステルアミド、ポリエーテル、ポリイミド、ポリアミドイミド、ポリスチレン、ポリカーボネート、ポリ-ρ-フェニレンスルフィド、ポリエーテルエステル、ポリ塩化ビニル、ポリ(メタ)アクリル酸エステルが挙げられる。また、これらの共重合体やブレンド物やさらに架橋した化合物を用いることもできる。
さらに、上記プラスチックフィルムの中でも、ポリエステル、例えば、ポリエチレンテレフタレート、ポリエチレン2,6-ナフタレート、ポリエチレンα,β-ビス(2-クロルフェノキシ)エタン4,4’-ジカルボキシレート、ポリブチレンテレフタレートなどからなるフィルムが好ましく、これらの中で機械的特性、作業性などの品質、経済性などを総合的に勘案すると、ポリエチレンテレフタレートからなるフィルムが特に好ましく用いられる。 There are no particular limitations on the form of the substrate A, cover material B, and cover material C used in the present invention, but for example, 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.
Furthermore, among the above-mentioned plastic films, polyester, for example, polyethylene terephthalate,
本発明で用いられる基材Aは、単層であることが好ましいが、例えば、隣接する樹脂層Xおよび/または樹脂層Yとの接着強度を向上することを目的とした厚み1μm以下の層(易接着層)を表層に有する、積層構成としてもよい。
カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間には、必要に応じて樹脂層X、Yとは異なる層を設けてもよい。異なる層の表面に、さらにコロナ放電処理や、プライマー処理等の表面処理を実施することにより、異なる層に積層させる樹脂層X、Yをより強固に形成することができる。他に、バイオセンサに用いる電極材料として機能させるために、カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間に、カーボンあるいは金、白金、パラジウムなどの貴金属からなる電極層を、スクリーン印刷を初めとする各種印刷法やスパッタリング蒸着法などの手段を用いて設けてもよい。カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間に設ける電極層には、測定電極、対電極、および検知電極を設けることが好ましい。また本発明の積層体をバイオセンサとして用いる場合には、この電極層上に、液体試料中の特定成分と特異的に反応する酵素、メディエータなどを含む試薬層を形成してもよい。 The base material A used in the present invention is preferably a single layer, but for example, a layer having a thickness of 1 μm 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.
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 layer different from the resin layers X and Y may be provided as necessary. . By further performing surface treatment such as corona discharge treatment or primer treatment on the surface of different layers, the resin layers X and Y to be laminated on different layers can be formed more firmly. Besides, carbon or gold, 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, in order to function as an electrode material used for a biosensor 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. . When the laminate of the present invention is used as a biosensor, 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.
カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間には、必要に応じて樹脂層X、Yとは異なる層を設けてもよい。異なる層の表面に、さらにコロナ放電処理や、プライマー処理等の表面処理を実施することにより、異なる層に積層させる樹脂層X、Yをより強固に形成することができる。他に、バイオセンサに用いる電極材料として機能させるために、カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間に、カーボンあるいは金、白金、パラジウムなどの貴金属からなる電極層を、スクリーン印刷を初めとする各種印刷法やスパッタリング蒸着法などの手段を用いて設けてもよい。カバー材料Bとそれに隣接する樹脂層Xとの間および/またはカバー材料Cとそれに隣接する樹脂層Yとの間に設ける電極層には、測定電極、対電極、および検知電極を設けることが好ましい。また本発明の積層体をバイオセンサとして用いる場合には、この電極層上に、液体試料中の特定成分と特異的に反応する酵素、メディエータなどを含む試薬層を形成してもよい。 The base material A used in the present invention is preferably a single layer, but for example, a layer having a thickness of 1 μm 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.
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 layer different from the resin layers X and Y may be provided as necessary. . By further performing surface treatment such as corona discharge treatment or primer treatment on the surface of different layers, the resin layers X and Y to be laminated on different layers can be formed more firmly. Besides, carbon or gold, 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, in order to function as an electrode material used for a biosensor 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. . When the laminate of the present invention is used as a biosensor, 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.
本発明の積層体は、バイオセンサとして好適に用いられる。したがって、本発明の積層体を有するバイオセンサは、積層体に加えて、試薬層および電極層を有する。
血糖値測定を例にとって、バイオセンサの使用方法を示す。上記構成のバイオセンサを測定機器本体に差し込んだ後、血液をバイオセンサのキャビティの開口部に接触させると、血液がキャビティの内部に吸引され、血液がキャビティの先端に配された試薬層に含まれる酵素と反応して、電流が発生する。この電流は、血液中の血糖値に対応しており、メディエータ、電極層を介して測定機器本体に伝えられ、測手機器本体に組み込まれた演算装置によって血糖値へ変換される。 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.
Taking a blood glucose level measurement as an example, 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.
血糖値測定を例にとって、バイオセンサの使用方法を示す。上記構成のバイオセンサを測定機器本体に差し込んだ後、血液をバイオセンサのキャビティの開口部に接触させると、血液がキャビティの内部に吸引され、血液がキャビティの先端に配された試薬層に含まれる酵素と反応して、電流が発生する。この電流は、血液中の血糖値に対応しており、メディエータ、電極層を介して測定機器本体に伝えられ、測手機器本体に組み込まれた演算装置によって血糖値へ変換される。 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.
Taking a blood glucose level measurement as an example, 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.
また、本発明の積層体は、基材Aのそれぞれの面に、樹脂層X、Yを介してそれぞれカバー材料Bおよびカバー材料Cを有する積層体であり、基材Aとともにカバー材料Cがキャビティの面を構成していてもよい。
また、図1に示すように、カバーフィルム5はカバー材料B21と樹脂層X31、またはカバー材料C22と樹脂層Y32の二層により構成することができる。図1の積層体6は、基材A1のそれぞれの面に、樹脂層X31、樹脂層Y32を介してそれぞれカバー材料B21およびカバー材料C22を有する積層体6であり、基材A1とともに樹脂層X31および樹脂層Y32がキャビティ4の面を構成している。
液体試料を導入するキャビティの面7a~10bは親水性を有することが好ましい。親水性とは、表面に水を滴下した際の水のぬれ広がりを表す尺度であり、親水性が高いと、通常の毛細管現象に加え、液体試料の表面張力低下の効果が相乗し、導入時間の短縮を図ることができる。そのため、積層体構成において、キャビティの面を構成する樹脂層(例えば、図1および図3の符号7aや図1の7b、図3の符号10aや10bで表される樹脂層)には、後述する手法にて高い親水性を付与することができる。また、キャビティを構成する5つの面のうち、親水性を有する面の面積割合が大きいほど、液体試料のキャビティへの導入速度が向上するため、基材Aの両面を先の親水性を有する樹脂層で構成することがより好ましい。すなわち、キャビティの少なくとも1つの面の全部又は一部が、樹脂層Xまたは樹脂層Yで形成されることが好ましい。ここで、「キャビティの少なくとも1つの面の全部又は一部が、樹脂層Xまたは樹脂層Yで形成される」とは、例えば図1の符号7aで示されるようなキャビティの5つの面のうち少なくとも1つの面が樹脂層で形成されている場合(キャビティの少なくとも1つの面の全部が、樹脂層Xまたは樹脂層Yで形成される態様)や、例えば図3の符号10aおよび10bで示されるような、キャビティの少なくとも1つの面が基材Aおよび樹脂層Yで形成されている場合(キャビティの少なくとも1つの面の一部が、樹脂層Xまたは樹脂層Yで形成される態様)をいう。 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.
Moreover, as shown in FIG. 1, thecover 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.
Thesurfaces 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. When hydrophilicity is high, in addition to normal capillary action, the effect of surface tension reduction of the liquid sample is synergistic, and the introduction time is Can be shortened. Therefore, in the laminate structure, 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. Moreover, since the introduction rate to the cavity of a liquid sample improves, so that the area ratio of the surface which has hydrophilicity is large among five surfaces which comprise a cavity, resin which has the hydrophilicity of the front of both surfaces of the base material A earlier More preferably, it is composed of layers. That is, it is preferable that all or part of at least one surface of the cavity be formed of the resin layer X or the resin layer Y. Here, “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. When 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. Such a case where at least one surface of the cavity is formed of the base material A and the resin layer Y (a mode in which a part of at least one surface of the cavity is formed of the resin layer X or the resin layer Y) .
また、図1に示すように、カバーフィルム5はカバー材料B21と樹脂層X31、またはカバー材料C22と樹脂層Y32の二層により構成することができる。図1の積層体6は、基材A1のそれぞれの面に、樹脂層X31、樹脂層Y32を介してそれぞれカバー材料B21およびカバー材料C22を有する積層体6であり、基材A1とともに樹脂層X31および樹脂層Y32がキャビティ4の面を構成している。
液体試料を導入するキャビティの面7a~10bは親水性を有することが好ましい。親水性とは、表面に水を滴下した際の水のぬれ広がりを表す尺度であり、親水性が高いと、通常の毛細管現象に加え、液体試料の表面張力低下の効果が相乗し、導入時間の短縮を図ることができる。そのため、積層体構成において、キャビティの面を構成する樹脂層(例えば、図1および図3の符号7aや図1の7b、図3の符号10aや10bで表される樹脂層)には、後述する手法にて高い親水性を付与することができる。また、キャビティを構成する5つの面のうち、親水性を有する面の面積割合が大きいほど、液体試料のキャビティへの導入速度が向上するため、基材Aの両面を先の親水性を有する樹脂層で構成することがより好ましい。すなわち、キャビティの少なくとも1つの面の全部又は一部が、樹脂層Xまたは樹脂層Yで形成されることが好ましい。ここで、「キャビティの少なくとも1つの面の全部又は一部が、樹脂層Xまたは樹脂層Yで形成される」とは、例えば図1の符号7aで示されるようなキャビティの5つの面のうち少なくとも1つの面が樹脂層で形成されている場合(キャビティの少なくとも1つの面の全部が、樹脂層Xまたは樹脂層Yで形成される態様)や、例えば図3の符号10aおよび10bで示されるような、キャビティの少なくとも1つの面が基材Aおよび樹脂層Yで形成されている場合(キャビティの少なくとも1つの面の一部が、樹脂層Xまたは樹脂層Yで形成される態様)をいう。 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.
Moreover, as shown in FIG. 1, the
The
本発明におけるキャビティは、上述したとおり液体試料を導入するための導入口を備えており、キャビティを構成する面が(i)樹脂層Xで構成される1面、(ii)樹脂層Yで構成される1面、(iii)基材Aのみで構成される3面から構成されるか、または、(iv)樹脂層Xで構成される1面、(v)基材Aおよび樹脂層Yのみで構成される3面、(vi)カバー材料Cで構成される1面から構成されるものである。キャビティが複数種類の面から構成されることで、それぞれの面の組成を調整することで、親水性を任意に調整し易くなる。また、キャビティを構成する面は、必ずしも平面でなくともよく、例えば湾曲したような曲面や、凹凸を有するような面も、キャビティを構成する面に含まれるものとする。
ここで、(i)および(iv)における「樹脂層Xで構成される1面」とは、図1および3の符号7aで示されるように、キャビティを構成する1面が樹脂層Xで構成されることをいう。同様に、(ii)における「樹脂層Yで構成される1面」とは、図1の符号7bで示されるように、キャビティを構成する1面が樹脂層Yで構成されることをいう。 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. When 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. In addition, 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.
Here, in the “one side composed of the resin layer X” in (i) and (iv), as shown byreference numeral 7 a in FIGS. It says to be done. Similarly, “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.
ここで、(i)および(iv)における「樹脂層Xで構成される1面」とは、図1および3の符号7aで示されるように、キャビティを構成する1面が樹脂層Xで構成されることをいう。同様に、(ii)における「樹脂層Yで構成される1面」とは、図1の符号7bで示されるように、キャビティを構成する1面が樹脂層Yで構成されることをいう。 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. When 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. In addition, 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.
Here, in the “one side composed of the resin layer X” in (i) and (iv), as shown by
(iii)における「基材Aのみで構成される3面」とは、図1の符号8aおよび8bで示されるように、キャビティを構成する3面が基材Aのみで構成されることをいう。このとき、例えば図6の符号12a、12bで示されるような基材A、樹脂層Xおよび樹脂層Yで構成される面は「基材Aのみで構成される3面」には該当しないものとする。
(v)における「基材Aおよび樹脂層Yのみで構成される3面」とは、図3の符号10aおよび10bで示されるように、キャビティを構成する3面が基材Aおよび樹脂層Yのみで構成されることをいう。このとき、例えば基材Aと樹脂層Yとの間に他の層を含むような構成は、キャビティを構成する3面が基材Aおよび樹脂層Y以外に当該他の層を含むことになるため、「基材Aおよび樹脂層Yのみで構成される3面」には該当しないものとする。 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. . At this time, for example, 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. At this time, for example, in a configuration including another layer between the base material A and the resin layer Y, 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."
(v)における「基材Aおよび樹脂層Yのみで構成される3面」とは、図3の符号10aおよび10bで示されるように、キャビティを構成する3面が基材Aおよび樹脂層Yのみで構成されることをいう。このとき、例えば基材Aと樹脂層Yとの間に他の層を含むような構成は、キャビティを構成する3面が基材Aおよび樹脂層Y以外に当該他の層を含むことになるため、「基材Aおよび樹脂層Yのみで構成される3面」には該当しないものとする。 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
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
(vi)における「カバー材料Cで構成される1面」とは、図3の符号9で示されるように、キャビティを構成する1面がカバー材料Cで構成されることをいう。
キャビティは、例えば基材Aの1層の構成を、あるいは、基材A、樹脂層X又は樹脂層Y、並びに後述するシリコーン系樹脂フィルムの3層が積層された構成を、垂直方向に加工することで設けるため、直方体形状であることが好ましい。キャビティの幅は、液体試料が毛細管現象にて安定かつ高速で導入される幅であることが望まれる。キャビティの幅は、液体試料の表面張力や基材Aの厚みにも依存するが、毛細管現象の効果を得るために50mmよりも小さいことが好ましい。また、液体試料を導入可能な幅が必要であることから、キャビティの幅は0.1mmよりも大きいことが好ましい。また、キャビティの長さに特に制限はないが、3mm以上20mm以下が好ましい。3mmよりも短いと検査時のばらつきが大きくなる場合がある。20mmよりも長いと液体試料の導入速度が安定しないばかりか、容積が大きいため必要な液体試料の量が多くなる場合がある。キャビティの平面方向の長さに特に制限はないが、液体試料の使用量を低減するために10mm以下とすることが好ましく、7mm以下とすることがより好ましい。 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 Preferably, 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. In addition, 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.
キャビティは、例えば基材Aの1層の構成を、あるいは、基材A、樹脂層X又は樹脂層Y、並びに後述するシリコーン系樹脂フィルムの3層が積層された構成を、垂直方向に加工することで設けるため、直方体形状であることが好ましい。キャビティの幅は、液体試料が毛細管現象にて安定かつ高速で導入される幅であることが望まれる。キャビティの幅は、液体試料の表面張力や基材Aの厚みにも依存するが、毛細管現象の効果を得るために50mmよりも小さいことが好ましい。また、液体試料を導入可能な幅が必要であることから、キャビティの幅は0.1mmよりも大きいことが好ましい。また、キャビティの長さに特に制限はないが、3mm以上20mm以下が好ましい。3mmよりも短いと検査時のばらつきが大きくなる場合がある。20mmよりも長いと液体試料の導入速度が安定しないばかりか、容積が大きいため必要な液体試料の量が多くなる場合がある。キャビティの平面方向の長さに特に制限はないが、液体試料の使用量を低減するために10mm以下とすることが好ましく、7mm以下とすることがより好ましい。 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 Preferably, 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. In addition, 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.
キャビティを有する基材Aの両面に設ける樹脂層X、Yは、主にそれぞれ基材Aとカバー材料Bを、または基材Aとカバー材料Cの2つのシートの面同士を接着するために用いられる。本発明に用いられる樹脂層X、Yには、組成・硬化方法・固形分量などは問わないが、基材Aおよびカバー材料Bに対し、十分な接着強度を発現することが好ましい。なお、基材Aの両面に設ける樹脂層X、Yは同一であってもよいし、異なっていてもよい。すなわち、基材Aの両面に設ける樹脂層X、Yはその組成・硬化方法・固形分量等が同一であってもよいし、それぞれの樹脂層X、Yが異なる組成等であってもよい。樹脂層X、Yの組成として例えば、その成分として粘着剤あるいはホットメルト接着剤を用いてもよい。
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. Be 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. As the composition of the resin layers X and Y, for example, an adhesive or a hot melt adhesive may be used as the component.
粘着剤は圧力を加えることで被着体を接着させる塗剤を指す一方、ホットメルト接着剤は加熱することで被着体を接着させる塗剤を指す。粘着剤およびホットメルト接着剤ともに、常温では固形・半固形、高温では液体となる熱可塑性樹脂を主成分とする接着剤であり、水や有機溶剤にて塗液として希釈された溶液状態であってもよい。ここでいう主成分とは、粘着剤あるいはホットメルト接着剤全体を100質量%としたとき80質量%以上を占める成分を指し、ホットメルト接着剤の特性に最も大きな影響を与える成分となり得る。
粘着剤あるいはホットメルト接着剤の主成分として使用できる熱可塑性樹脂には、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1種の樹脂を含むことが好ましい。特にホットメルト接着剤は熱硬化性樹脂と比べて低温で溶融するため、積層体に使用される他の部材への熱影響を小さく抑えることができる。また、冷却固化であるため、短時間で接合が可能であり作業性が向上される。 The adhesive refers to a coating that adheres an adherend by applying pressure, while 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 The term "main component" as used herein 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 thermoplastic resins that can be used as the main component of the pressure-sensitive adhesive or hot melt adhesive include polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin and acrylic urethane It is preferable to include at least one resin selected from the group consisting of resins. In particular, since 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. In addition, because of cooling and solidification, bonding can be performed in a short time, and the workability can be improved.
粘着剤あるいはホットメルト接着剤の主成分として使用できる熱可塑性樹脂には、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1種の樹脂を含むことが好ましい。特にホットメルト接着剤は熱硬化性樹脂と比べて低温で溶融するため、積層体に使用される他の部材への熱影響を小さく抑えることができる。また、冷却固化であるため、短時間で接合が可能であり作業性が向上される。 The adhesive refers to a coating that adheres an adherend by applying pressure, while 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 The term "main component" as used herein 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 thermoplastic resins that can be used as the main component of the pressure-sensitive adhesive or hot melt adhesive include polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin and acrylic urethane It is preferable to include at least one resin selected from the group consisting of resins. In particular, since 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. In addition, because of cooling and solidification, bonding can be performed in a short time, and the workability can be improved.
ホットメルト接着剤は、例えば樹脂層(ホットメルト接着剤)を介して基材Aとカバー材料Bを配し、ヒートシーラーを用いて、シール温度120℃、シール時間1.0秒、シール圧力0.2MPaの条件で基材Aとカバー材料Bを接着させる。本発明の積層体について、JIS Z0237:2009に従い、はく離速度50mm/分、90°はく離による基材Aと樹脂層Yとの接着強度を3回評価し、その平均値を結果とした場合、2.5N/10mm以上の接着強度を示すことが好ましく、5N/10mm以上の接着強度を示すことがより好ましい。接着強度が2.5N/10mm未満であると安定した接合をすることができない場合があり、積層体の取り扱いによって端部から積層体の剥離が発生する場合がある。
本発明で用いられる樹脂層Xおよび/または樹脂層Yは、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1つの樹脂を含有することが好ましい。さらに樹脂層Xおよび/または樹脂層Yに親水性を付与させる場合には界面活性剤を含有することが好ましい。用いられる界面活性剤に制限はないが、ポリアルキレングリコール骨格を有する非イオン性の界面活性剤を含有させることが好ましい(以下、ポリアルキレングリコール骨格を有する非イオン性の界面活性剤を単に界面活性剤ということもある)。 For the hot melt adhesive, for example, 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. For the laminate of the present invention, 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. If the adhesive strength is less than 2.5 N / 10 mm, stable bonding may not be possible, and peeling of the laminate from the end may occur due to the handling of the laminate.
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. Although there is no limitation on the surfactant to be used, it is preferable to contain a nonionic surfactant having a polyalkylene glycol skeleton (hereinafter, nonionic surfactant having a polyalkylene glycol skeleton is simply used as a surfactant). Sometimes called an agent).
本発明で用いられる樹脂層Xおよび/または樹脂層Yは、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1つの樹脂を含有することが好ましい。さらに樹脂層Xおよび/または樹脂層Yに親水性を付与させる場合には界面活性剤を含有することが好ましい。用いられる界面活性剤に制限はないが、ポリアルキレングリコール骨格を有する非イオン性の界面活性剤を含有させることが好ましい(以下、ポリアルキレングリコール骨格を有する非イオン性の界面活性剤を単に界面活性剤ということもある)。 For the hot melt adhesive, for example, 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. For the laminate of the present invention, 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. If the adhesive strength is less than 2.5 N / 10 mm, stable bonding may not be possible, and peeling of the laminate from the end may occur due to the handling of the laminate.
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. Although there is no limitation on the surfactant to be used, it is preferable to contain a nonionic surfactant having a polyalkylene glycol skeleton (hereinafter, nonionic surfactant having a polyalkylene glycol skeleton is simply used as a surfactant). Sometimes called an agent).
まず、積層体を構成するホットメルト接着剤としては、先の群の中でもポリエステル樹脂または(メタ)アクリル樹脂をホットメルト接着剤として使用することが、基材A、カバー材料B、カバー材料Cとの接着強度や、耐熱性などの観点から好ましい。さらに融点が40℃以上150℃以下のポリエステル樹脂または(メタ)アクリル樹脂をホットメルト接着剤として使用することが特に好ましい。融点が40℃未満であると、熱接着時にホットメルト接着剤が流動してしまうことで接着させたくない部分にまで接着剤が流れ、接着させてしまう場合があり、150℃よりも大きいと、熱接着の際に高い温度をかけないと、接着させることができなくなることがあって、作業効率が低下したり、被接着体である基材A、カバー材料B、カバー材料Cが熱で損傷したりしてしまう場合がある。また、ホットメルト接着剤は、樹脂の凝集力が向上し、樹脂層の接着強度が向上するため芳香族骨格を有することが好ましい。また、ホットメルト接着剤として上述した樹脂を1種類のみ用いてもよいし、複数の樹脂を用いてもよい。
First, as 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. If it is greater than 150 ° C., If high temperature is not applied during thermal bonding, bonding may not be possible, resulting in reduced work efficiency or damage to the substrates A, cover material B, and cover material C, which are adherends, due to heat. You may be 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.
さらに、本発明における樹脂層Xおよび/または樹脂層Yは、上述したホットメルト接着剤とともにポリアルキレングリコール骨格を有する非イオン性の界面活性剤を含有することが好ましい。本発明に用いるポリアルキレングリコール骨格を有する非イオン性の界面活性剤は、親水性置換基としてポリアルキレングリコール骨格を有するとともに、疎水性置換基として後述する骨格を併せて有する。ここで、ポリアルキレングリコール骨格を有する非イオン性の界面活性剤としては、例えば、ポリオキシエチレンラウリル-硫酸エステルナトリウム塩等のポリオキシエチレン-アルキル硫酸エステル-ナトリウム塩、ポリオキシエチレン-ラウリルエーテル、ポリオキシエチレン-セチルエーテル、ポリオキシエチレン-オレイルエーテル、ポリオキシエチレン-ステアリルエーテル、ポリオキシエチレン-2-エチルヘキシルエーテル、ポリオキシエチレン-イソデシルエーテル等のポリオキシエチレン-アルキルエーテル、
ポリオキシエチレン-モノラウレート、ポリオキシエチレン-モノステアレート、ポリオキシエチレン-モノオレート等のポリオキシエチレン-アルキルエステル、ポリオキシエチレンソルビタン-モノラウレート、ポリオキシエチレンソルビタン-モノステアレート、ポリオキシエチレンソルビタン-モノオレート、ポリオキシエチレンソルビタン-モノオレート等のソルビタンエステル・エチレンオキシド付加型、
ポリオキシエチレン-ヤシ脂肪酸グリセリル等のモノグリセライド・エチレンオキシド付加型、
ポリオキシエチレン-硬化ヒマシ油等のトリグリセライド・エチレンオキシド付加型、
ポリオキシエチレン-ラウリルアミン、ポリオキシエチレン-アルキル(ヤシ)アミン、ポリオキシエチレン-ステアリルアミン、ポリオキシエチレン-オレイルアミン、ポリオキシエチレン-牛脂アルキルアミン、ポリオキシエチレンアルキル-プロピレンジ゛アミン等のアルキルポリエーテルアミン型
ポリオキシエチレン-モノメチルエーテル、ポリオキシエチレン-ジメチルエーテル、ポリオキシエチレン-グリセリルエーテル、ポリオキシエチレン・α,ω-ビス-3-アミノプロピル-エーテル、ポリエチレングリコール-ポリプロピレングリコール-ポリエチレングリコール(ブロックコポリマー)などの界面活性剤が挙げられるが、本発明に用いることができるポリアルキレングリコール骨格を有する非イオン性の界面活性剤はこの限りでない。 Furthermore, it is preferable that 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. Here, as the 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 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-dimethyl ether, polyoxyethylene-glyceryl ether, polyoxyethylene · α, ω-bis-3-aminopropyl-ether, polyethylene glycol-polypropylene glycol-polyethylene glycol ( Surfactants such as block copolymers), but nonionic surfactants having a polyalkylene glycol backbone that can be used in the present invention are It is not this limitation.
ポリオキシエチレン-モノラウレート、ポリオキシエチレン-モノステアレート、ポリオキシエチレン-モノオレート等のポリオキシエチレン-アルキルエステル、ポリオキシエチレンソルビタン-モノラウレート、ポリオキシエチレンソルビタン-モノステアレート、ポリオキシエチレンソルビタン-モノオレート、ポリオキシエチレンソルビタン-モノオレート等のソルビタンエステル・エチレンオキシド付加型、
ポリオキシエチレン-ヤシ脂肪酸グリセリル等のモノグリセライド・エチレンオキシド付加型、
ポリオキシエチレン-硬化ヒマシ油等のトリグリセライド・エチレンオキシド付加型、
ポリオキシエチレン-ラウリルアミン、ポリオキシエチレン-アルキル(ヤシ)アミン、ポリオキシエチレン-ステアリルアミン、ポリオキシエチレン-オレイルアミン、ポリオキシエチレン-牛脂アルキルアミン、ポリオキシエチレンアルキル-プロピレンジ゛アミン等のアルキルポリエーテルアミン型
ポリオキシエチレン-モノメチルエーテル、ポリオキシエチレン-ジメチルエーテル、ポリオキシエチレン-グリセリルエーテル、ポリオキシエチレン・α,ω-ビス-3-アミノプロピル-エーテル、ポリエチレングリコール-ポリプロピレングリコール-ポリエチレングリコール(ブロックコポリマー)などの界面活性剤が挙げられるが、本発明に用いることができるポリアルキレングリコール骨格を有する非イオン性の界面活性剤はこの限りでない。 Furthermore, it is preferable that 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. Here, as the 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 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-dimethyl ether, polyoxyethylene-glyceryl ether, polyoxyethylene · α, ω-bis-3-aminopropyl-ether, polyethylene glycol-polypropylene glycol-polyethylene glycol ( Surfactants such as block copolymers), but nonionic surfactants having a polyalkylene glycol backbone that can be used in the present invention are It is not this limitation.
ポリアルキレングリコール骨格を有する非イオン性の界面活性剤のうちより好ましくは疎水性置換基としてアルキル置換基を有する化合物が好ましい。市販されている具体例として、
パイオニンD-1004、パイオニンD-1007、パイオニンD-1706-N、パイオニンD-1715-N、パイオニンD-1105、パイオニンD-1110、パイオニンD-1103-D、パイオニンD-1105-D、パイオニンD-1103-S、パイオニンD-1105-S、パイオニンD-1107-S、パイオニンD-1109-S、パイオニンD-1004、パイオニンD-1004、パイオニンD-1004、
ニューカルゲンD-1203、ニューカルゲンD-1205、ニューカルゲンD-1208、パイオニンD-1305-Z、パイオニンD-1323-Z、パイオニンD-1803、パイオニンD-1402、パイオニンD-1420、パイオニンD-1504、パイオニンD-1508、パイオニンD-1518、パイオニンD-1106DIR、パイオニンD-1110DIR、パイオニンD-1107SP3、パイオニンD-1301-P、パイオニンD-1305-P(以上、竹本油脂株式会社製)、
エマルゲン102KG、エマルゲン103、エマルゲン104P、エマルゲン105、エマルゲン106、エマルゲン108、エマルゲン109P、エマルゲン120、エマルゲン123P、エマルゲン130K、エマルゲン147、エマルゲン150、エマルゲン210P、エマルゲン220、エマルゲン306P、エマルゲン320P、エマルゲン350、エマルゲン404、エマルゲン408、エマルゲン409PV、エマルゲン420、エマルゲン430、エマルゲン705、エマルゲン707、エマルゲン709、エマルゲン1108、エマルゲン1118S-70、エマルゲン1135S-70、エマルゲン1150S-60、エマルゲン2020G-HA、エマルゲン2025G(以上、花王株式会社製)、等が挙げられる。疎水性置換基がアルキル基であるとアルキル基の炭素数が異なる界面活性剤の製造・入手が容易であるため、後述するHLB値を任意に変更できるという利点がある。 Among the nonionic surfactants having a polyalkylene glycol backbone, compounds having an alkyl substituent as a hydrophobic substituent are more preferable. As a concrete example marketed,
Pionin D-1004, Pionin D-1007, Pionin D-1706-N, Pionin D-1715-N, Pionin D-1105, Pionin D-1110, Pionin D-1103-D, Pionin D-1105-D, Pionin D -1103-S, Pionin D-1105-S, Pionin D-1107-S, Pionin D-1109-S, Pionin D-1004, Pionin D-1004, Pionin D-1004,
Newkalgen D-1203, Neucalgen D-1205, Neucalgen D-1208, Pyonin D-1305-Z, Pionin D-1323-Z, Pionin D-1803, Pionin D-1402, Pionin D-1420, Pionin D- 1504, Pionin D-1508, Pionin D-1518, Pionin D-1106 DIR, Pionin D-1110 DIR, Pionin D-1107 SP3, Pionin D-1301-P, Pionin D-1305-P (all manufactured by Takemoto Yushi Co., Ltd.),
Emulgen 102 Kg, Emulgen 103, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109 P, Emulgen 120 P, Emulgen 123 P, Emulgen 130 K, Emulgen 147, Emulgen 150, Emulgen 210 P, Emulgen 220 P, Emulgen 306 P, Emulgen 350 P , Emulgen 404, Emulgen 408, Emulgen 409, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118 S-70, Emulgen 1135 S-70, Emulgen 1150 S-60, Emulgen 2020 G-HA, Emulgen 2025 G (As described above, manufactured by Kao Corporation), and the like. When the hydrophobic substituent is an alkyl group, it is easy to manufacture and obtain a surfactant having a different carbon number of the alkyl group, so that there is an advantage that the HLB value described later can be arbitrarily changed.
パイオニンD-1004、パイオニンD-1007、パイオニンD-1706-N、パイオニンD-1715-N、パイオニンD-1105、パイオニンD-1110、パイオニンD-1103-D、パイオニンD-1105-D、パイオニンD-1103-S、パイオニンD-1105-S、パイオニンD-1107-S、パイオニンD-1109-S、パイオニンD-1004、パイオニンD-1004、パイオニンD-1004、
ニューカルゲンD-1203、ニューカルゲンD-1205、ニューカルゲンD-1208、パイオニンD-1305-Z、パイオニンD-1323-Z、パイオニンD-1803、パイオニンD-1402、パイオニンD-1420、パイオニンD-1504、パイオニンD-1508、パイオニンD-1518、パイオニンD-1106DIR、パイオニンD-1110DIR、パイオニンD-1107SP3、パイオニンD-1301-P、パイオニンD-1305-P(以上、竹本油脂株式会社製)、
エマルゲン102KG、エマルゲン103、エマルゲン104P、エマルゲン105、エマルゲン106、エマルゲン108、エマルゲン109P、エマルゲン120、エマルゲン123P、エマルゲン130K、エマルゲン147、エマルゲン150、エマルゲン210P、エマルゲン220、エマルゲン306P、エマルゲン320P、エマルゲン350、エマルゲン404、エマルゲン408、エマルゲン409PV、エマルゲン420、エマルゲン430、エマルゲン705、エマルゲン707、エマルゲン709、エマルゲン1108、エマルゲン1118S-70、エマルゲン1135S-70、エマルゲン1150S-60、エマルゲン2020G-HA、エマルゲン2025G(以上、花王株式会社製)、等が挙げられる。疎水性置換基がアルキル基であるとアルキル基の炭素数が異なる界面活性剤の製造・入手が容易であるため、後述するHLB値を任意に変更できるという利点がある。 Among the nonionic surfactants having a polyalkylene glycol backbone, compounds having an alkyl substituent as a hydrophobic substituent are more preferable. As a concrete example marketed,
Pionin D-1004, Pionin D-1007, Pionin D-1706-N, Pionin D-1715-N, Pionin D-1105, Pionin D-1110, Pionin D-1103-D, Pionin D-1105-D, Pionin D -1103-S, Pionin D-1105-S, Pionin D-1107-S, Pionin D-1109-S, Pionin D-1004, Pionin D-1004, Pionin D-1004,
Newkalgen D-1203, Neucalgen D-1205, Neucalgen D-1208, Pyonin D-1305-Z, Pionin D-1323-Z, Pionin D-1803, Pionin D-1402, Pionin D-1420, Pionin D- 1504, Pionin D-1508, Pionin D-1518, Pionin D-1106 DIR, Pionin D-1110 DIR, Pionin D-1107 SP3, Pionin D-1301-P, Pionin D-1305-P (all manufactured by Takemoto Yushi Co., Ltd.),
Emulgen 102 Kg, Emulgen 103, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109 P, Emulgen 120 P, Emulgen 123 P, Emulgen 130 K, Emulgen 147, Emulgen 150, Emulgen 210 P, Emulgen 220 P, Emulgen 306 P, Emulgen 350 P , Emulgen 404, Emulgen 408, Emulgen 409, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118 S-70, Emulgen 1135 S-70, Emulgen 1150 S-60, Emulgen 2020 G-HA, Emulgen 2025 G (As described above, manufactured by Kao Corporation), and the like. When the hydrophobic substituent is an alkyl group, it is easy to manufacture and obtain a surfactant having a different carbon number of the alkyl group, so that there is an advantage that the HLB value described later can be arbitrarily changed.
上記ポリアルキレングリコール骨格を有する非イオン性の界面活性剤で示される化合物のうち、疎水性置換基として芳香族を含むアリルフェニル基を有するアリルフェニルエーテル型化合物で市販されている具体例として、パイオニンD-6112、ニューカルゲンC-150、ニューカルゲンC-173、ニューカルゲンC-200、ニューカルゲンC-314、ニューカルゲンCP-50、ニューカルゲンCP-80、ニューカルゲンCP-120、ニューカルゲンCP-15-200、パイオニンD-6512、パイオニンD-6414、DTD-51、パイオニンD-6315、ニューカルゲンE-200、パイオニンD-7240(以上、竹本油脂株式会社製)、等が挙げられる。疎水性置換基がアリルフェニル基であると、例えば芳香族を有するホットメルト接着剤を併用した場合に、ホットメルト接着剤と界面活性剤の芳香環のスタッキングによる凝集力向上効果によって、樹脂層の接着強度が向上するため好ましい。また、疎水性置換基がアリルフェニル基であると、アリルフェニル基の繰り返し数を任意に調整した界面活性剤の製造・入手が容易であるため、後述するHLB値を任意に変更できるという利点がある。
Among the compounds represented by the nonionic surfactant having a polyalkylene glycol skeleton, pionine is a commercially available example of an allylphenyl ether type compound having an arylphenyl group containing an aromatic group as a hydrophobic substituent. D-6112, Neucalgen C-150, Neucalgen C-173, Neucalgen C-200, Neucalgen C-314, Neucalgen CP-50, Neucalgen CP-80, Neucalgen CP-120, Neucalgen CP- 15-200, Pionin D-6512, Pionin D-6414, DTD-51, Pionin D-6315, Neucalgen E-200, Pionin D-7240 (all manufactured by Takemoto Yushi Co., Ltd.), and the like. When the hydrophobic substituent is an allylphenyl group, for example, when a hot melt adhesive having an aromatic group is used in combination, the cohesive strength of the resin layer is improved by the stacking of the hot melt adhesive and the aromatic ring of the surfactant. It is preferable because the adhesive strength is improved. In addition, when the hydrophobic substituent is an allylphenyl group, it is easy to manufacture and obtain a surfactant in which the repeating number of the allylphenyl group is arbitrarily adjusted, so that the HLB value described later can be arbitrarily changed. is there.
上記ポリアルキレングリコール骨格を有する非イオン性の界面活性剤で示される化合物のうち、ソルビタン脂肪酸誘導体で市販されている具体例として、レオドールTW-L120、レオドールTW-L106、レオドールTW-P120、レオドールTW-S120V、レオドールTW-S106V、レオドールTW-S-320V、レオドールTW-O120V、レオドールTW-O106V、レオドールTW-O320V、レオドールTW-IS399C、レオドールスーパーTW-L120(以上、花王株式会社製)、パイオニンD-941、パイオニンD-945、パイオニンD-945T(以上、竹本油脂株式会社製)等が挙げられる。
Among the compounds represented by nonionic surfactants having the above polyalkylene glycol skeleton, specific examples of commercially available 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.
前記積層体を構成する前記ポリアルキレングリコール骨格を有する非イオン性の界面活性剤の数平均分子量(Mn)は、好ましくは500~20,000、より好ましくは2,000~20,000、特に好ましくは5,000~18,000である。すなわち、かかる数平均分子量が500以上だと該積層体のロール加工に際しその搬送工程や印刷加工工程、またスリット加工工程をなどにおいて、搬送ロールやスリット刃表面や断面に界面活性剤成分が付着することを良好に防止することができ、その結果、各工程の清掃頻度が格段に減少するので好ましい。かかる数平均分子量が20,000以下であると、界面活性剤を樹脂層に均一に分散させやすくなるので好ましい。
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.
また、樹脂層Xや樹脂層Yに含まれる界面活性剤の融点または凝固点は、特に制限されるものではないが、30℃以下であるものが好ましい。融点または凝固点は、より好ましくは、25℃以下であり、更に好ましくは、20℃以下である。融点または凝固点が30℃より大きいと、樹脂層から前記界面活性剤がブリードアウトしやすくなり、ホットメルト接着剤の接着強度がばらつくことで接着強度の低下を招く場合がある。また、融点または凝固点が30℃以下であると、ホットメルト接着剤と界面活性剤を混合した塗布液を調合する際に界面活性剤の加熱溶解作業が不要となるため作業容易性の観点から好ましい。
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. Moreover, when preparing the coating liquid which mixed the hot melt adhesive and surfactant as melting | fusing point or freezing point is 30 degrees C or less, since the heating-melting operation | work of surfactant becomes unnecessary, it is preferable from a viewpoint of workability | operativity .
本発明における樹脂層Xおよび/または樹脂層Yは、樹脂層Xおよび樹脂層Yそれぞれについて樹脂層Xや樹脂層Yに含まれる樹脂100質量部に対し、界面活性剤の量が0.1~20質量部であるものが好ましく、より好ましくは、0.1~12質量部であり、さらに好ましくは、1~10質量部である。界面活性剤の量が0.1質量部未満であると、樹脂層の親水性が十分に得られず、液体試料の導入性が十分に発揮されない場合がある。また、積層体搬送工程やスリット工程などで樹脂層に含まれる主成分が付着することを防止する効果が十分に発揮されない場合がある。
界面活性剤の量が20質量部より大きいとホットメルト接着剤との十分な相溶性を得にくく、樹脂層表面にブリードアウトする界面活性剤が多くなりホットメルト接着剤の接着性が損なわれ、所望の接着強度を得られなくなる場合がある。また、界面活性剤の量が20質量部より大きいと界面活性剤のブリードアウトにより積層体搬送工程やスリット工程などで界面活性剤成分が付着し、加工工程の汚染が発生する場合がある。また、界面活性剤の量が20質量部より大きいとホットメルト接着剤の配合比が低下するため樹脂層の強度が低下し、安定した製膜が難しくなるばかりでなく、ホットメルト接着剤と界面活性剤を混合した塗料の貯蔵安定性の低下を招く場合がある。界面活性剤の量が0.1~20質量部であると、上記の欠点を解決した樹脂層を得ることができるため好ましい。 In the resin layer X and / or the resin layer Y in the present invention, 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.
When 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. In addition, if 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.
界面活性剤の量が20質量部より大きいとホットメルト接着剤との十分な相溶性を得にくく、樹脂層表面にブリードアウトする界面活性剤が多くなりホットメルト接着剤の接着性が損なわれ、所望の接着強度を得られなくなる場合がある。また、界面活性剤の量が20質量部より大きいと界面活性剤のブリードアウトにより積層体搬送工程やスリット工程などで界面活性剤成分が付着し、加工工程の汚染が発生する場合がある。また、界面活性剤の量が20質量部より大きいとホットメルト接着剤の配合比が低下するため樹脂層の強度が低下し、安定した製膜が難しくなるばかりでなく、ホットメルト接着剤と界面活性剤を混合した塗料の貯蔵安定性の低下を招く場合がある。界面活性剤の量が0.1~20質量部であると、上記の欠点を解決した樹脂層を得ることができるため好ましい。 In the resin layer X and / or the resin layer Y in the present invention, 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.
When 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. In addition, if 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.
ホットメルト接着剤としては、例えば、アロンメルトPES-120L、PES-140H、PES-111EE、PES310S30、PES375S40、PPET1008、PPET1025、PPET2102、PPET1303S(以上、東亞合成株式会社製)、Y-167、H-930-S、H-180S(以上、田中ケミカル株式会社製)、ニチゴーポリエスター(R)SP-154、SP-165、SP-170、SP-176、SP-180、SP-182、SP-185(以上、日本合成化学株式会社製)、バイロン(R)200、240、300、550、BX1001(以上、東洋紡株式会社製)、ポリゾール(R)SE-1720、SE-4210E、SE-6210、SE-6210L(以上、昭和電工株式会社製)などが挙げられる。
As 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.
本発明における樹脂層X、樹脂層Yの少なくとも一方の樹脂層の表面の水接触角は15度未満であることが好ましい。水に対する接触角が15度未満であることにより液体試料の高速かつ安定した導入を十分に実現することができるため好ましい。樹脂層X、樹脂層Yの少なくとも一方の樹脂層の表面の水接触角が15度未満であれば好ましく、両方の樹脂層の表面の水接触角が15度未満であることがより好ましい。
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.
本発明に用いる界面活性剤は、HLB値が8~15の界面活性剤であることが好ましい。HLB値が8~15の界面活性剤を用いることでホットメルト接着剤との相溶性を保ちつつ、樹脂層に親水性を与えることができるため好ましい。
HLB(HyDrophile-Lipophile Balance)値とは、親水親油バランスのことであり、下記式(1)から求められるグリフィン法(全訂版 新・界面活性剤入門 p128)により算出した値である。
界面活性剤のHLB値=(親水基部分の数平均分子量/界面活性剤の数平均分子量)×20 式(1)
界面活性剤のHLB値が15より大きい場合、界面活性剤と樹脂層の主成分との十分な相溶性を得にくく、樹脂層の表面にブリードアウトする界面活性剤が多くなりホットメルト接着剤の接着性が損なわれ、所望の接着強度を得られなくなる場合がある。一方で、界面活性剤のHLB値が8より小さい場合、樹脂層の親水性が十分に得られなくなる場合がある。界面活性剤のHLB値が8~15であると、ホットメルト接着剤との相溶性および樹脂層の親水性の両立が可能であるため好ましい。 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)
When the 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. On the other hand, when 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.
HLB(HyDrophile-Lipophile Balance)値とは、親水親油バランスのことであり、下記式(1)から求められるグリフィン法(全訂版 新・界面活性剤入門 p128)により算出した値である。
界面活性剤のHLB値=(親水基部分の数平均分子量/界面活性剤の数平均分子量)×20 式(1)
界面活性剤のHLB値が15より大きい場合、界面活性剤と樹脂層の主成分との十分な相溶性を得にくく、樹脂層の表面にブリードアウトする界面活性剤が多くなりホットメルト接着剤の接着性が損なわれ、所望の接着強度を得られなくなる場合がある。一方で、界面活性剤のHLB値が8より小さい場合、樹脂層の親水性が十分に得られなくなる場合がある。界面活性剤のHLB値が8~15であると、ホットメルト接着剤との相溶性および樹脂層の親水性の両立が可能であるため好ましい。 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)
When the 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. On the other hand, when 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.
また、樹脂層X、樹脂層Yの付着量は、片面1~50g/m2であることが好ましく、より好ましくは2~30g/m2である。付着量が1g/m2より少ないと加工時の擦り傷等により付着層の脱落や、ピンホールが発生したり、所望の接着強度を得られなくなったりする場合がある。その結果、接着強度のバラツキが発生する場合がある。また、付着量が50g/m2より多くなると、積層体搬送工程やスリット工程などでホットメルト接着剤成分が付着することを防止する効果が小さくなる場合がある。
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.
次に本発明の積層体を製造する手段について、以下説明する。樹脂層X、樹脂層Yは、例えば該樹脂層を構成する成分を含む塗布液を、カバー材料B、カバー材料Cに塗布し、塗膜とすることで形成することができる。親水性を付与する場合、かかる塗布液は、例えば、ホットメルト接着剤と界面活性剤を混合したもの、あるいはそれを熱溶融して得ることができる。
該塗布液の塗布方法は特に限定されないが、グラビアコート法、リバースコート法、キスコート法、ダイコート法、およびバーコート法などの方法を用いることができる。なお、塗布液濃度、塗膜乾燥条件または、塗膜の冷却条件は特に限定されるものではないが、塗膜乾燥条件は基材の諸特性に悪影響を及ぼさない範囲で行なうことが望ましい。 Next, means for producing the laminate of the present invention will be described below. 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. In the case of imparting hydrophilicity, 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. Although the 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.
該塗布液の塗布方法は特に限定されないが、グラビアコート法、リバースコート法、キスコート法、ダイコート法、およびバーコート法などの方法を用いることができる。なお、塗布液濃度、塗膜乾燥条件または、塗膜の冷却条件は特に限定されるものではないが、塗膜乾燥条件は基材の諸特性に悪影響を及ぼさない範囲で行なうことが望ましい。 Next, means for producing the laminate of the present invention will be described below. 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. In the case of imparting hydrophilicity, 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. Although the 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.
また、本発明の樹脂層X、樹脂層Yは、例えば上記塗布液で予め膜状物を作り、それをカバー材料Bまたはカバー材料Cに貼合することで形成することもできる。貼合する場合は、例えばシリコーン系樹脂フィルム等の離型フィルムに塗布液を塗工し、カバー材料に転写する方法が採用される(以降、カバー材料と樹脂層の二層構成体をカバーフィルムと呼ぶ場合がある。)。
次に、厚み方向に貫通した貫通孔を有する基材Aと、先に形成した樹脂層X、樹脂層Yとを合わせ、熱処理をすることで接着する、熱処理の方法は特に限定されないが、加熱プレスやヒートシーラー(加熱ローラー)を用いることもできる。その後、先の基材Aの裏面にも別途準備したカバー材料Bまたはカバー材料Cを、熱処理により貼合することで、本発明の積層体を得ることができる。なお、厚み方向に貫通した貫通孔を樹脂層X、樹脂層Yと基材Aに同時に設ける場合には、上記塗布液はカバー材料Bまたはカバー材料Cではなく基材Aに形成し、基材A側の面にカバーフィルムを、樹脂層側に別のカバー材料を熱処理により貼合することで積層体を得る。 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. In the case of 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).
Next, although 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 (heating roller) can also be used. Then, 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. When the through holes penetrating in the thickness direction are simultaneously provided in the resin layer X and the resin layer Y and the base material A, 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.
次に、厚み方向に貫通した貫通孔を有する基材Aと、先に形成した樹脂層X、樹脂層Yとを合わせ、熱処理をすることで接着する、熱処理の方法は特に限定されないが、加熱プレスやヒートシーラー(加熱ローラー)を用いることもできる。その後、先の基材Aの裏面にも別途準備したカバー材料Bまたはカバー材料Cを、熱処理により貼合することで、本発明の積層体を得ることができる。なお、厚み方向に貫通した貫通孔を樹脂層X、樹脂層Yと基材Aに同時に設ける場合には、上記塗布液はカバー材料Bまたはカバー材料Cではなく基材Aに形成し、基材A側の面にカバーフィルムを、樹脂層側に別のカバー材料を熱処理により貼合することで積層体を得る。 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. In the case of 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).
Next, although 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 (heating roller) can also be used. Then, 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. When the through holes penetrating in the thickness direction are simultaneously provided in the resin layer X and the resin layer Y and the base material A, 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.
以下に本発明を実施例により具体的に説明を行なうが、本発明はこれらの実施例により限定されるものではない。なお、実施例において、試験片の特性の評価方法は、以下のとおりである。
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. In addition, in the Example, the evaluation method of the characteristic of a test piece is as follows.
〔樹脂層の表面の水に対する接触角〕
樹脂層の水に対する接触角は、DM-400s(協和界面科学株式会社製)を用い、純水(2.0μl)を樹脂層の表面に滴下した際にできる液滴に対し、滴下5秒後における樹脂層の表面の水接触角について5回測定を行い、その平均値を結果とした。 [Contact angle of the surface of the resin layer to water]
The contact angle of the resin layer to water is 5 seconds after dropping of pure water (2.0 μl) 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.
樹脂層の水に対する接触角は、DM-400s(協和界面科学株式会社製)を用い、純水(2.0μl)を樹脂層の表面に滴下した際にできる液滴に対し、滴下5秒後における樹脂層の表面の水接触角について5回測定を行い、その平均値を結果とした。 [Contact angle of the surface of the resin layer to water]
The contact angle of the resin layer to water is 5 seconds after dropping of pure water (2.0 μl) 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.
〔樹脂層の接着強度〕
積層体について、樹脂層を設けたカバー材料と、基材AとをJIS Z0237:2009に従い、引きはがし角度90°、はく離速度50mm/分の条件にて接着強度を3回評価し、その平均値を結果とした。 [Adhesive strength of resin layer]
For the laminate, 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.
積層体について、樹脂層を設けたカバー材料と、基材AとをJIS Z0237:2009に従い、引きはがし角度90°、はく離速度50mm/分の条件にて接着強度を3回評価し、その平均値を結果とした。 [Adhesive strength of resin layer]
For the laminate, 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.
〔樹脂の数平均分子量〕
GPCを用い、次の条件にてポリスチレン基準の分子量を算出した。装置:HLC-8220GPC(東ソー社製)、カラム:TSKgel GMHXL 2本(東ソー社製)、カラム温度:40℃、溶離液:テトラヒドロフラン 1.00ml/分、検出器:RI。 [Number average molecular weight of resin]
The molecular weight of polystyrene standard was computed on condition of the following using GPC. Apparatus: HLC-8220GPC (manufactured by Tosoh Corp.), column: TSKgel GMHXL 2 (manufactured by Tosoh Corp.), column temperature: 40 ° C., eluent: tetrahydrofuran 1.00 ml / min, detector: RI.
GPCを用い、次の条件にてポリスチレン基準の分子量を算出した。装置:HLC-8220GPC(東ソー社製)、カラム:TSKgel GMHXL 2本(東ソー社製)、カラム温度:40℃、溶離液:テトラヒドロフラン 1.00ml/分、検出器:RI。 [Number average molecular weight of resin]
The molecular weight of polystyrene standard was computed on condition of the following using GPC. Apparatus: HLC-8220GPC (manufactured by Tosoh Corp.), column: TSKgel GMHXL 2 (manufactured by Tosoh Corp.), column temperature: 40 ° C., eluent: tetrahydrofuran 1.00 ml / min, detector: RI.
〔樹脂層の付着量〕
塗布液を塗布した基材100cm2の質量を測定し(X)、次に塗布前の基材100cm2の質量を測定し(Y)、(X-Y)×100で付着量(g/m2)を算出した。 [Attached amount of resin layer]
The mass of the substrate 100 cm 2 coated with the coating solution is measured (X), and then the mass of the substrate 100 cm 2 before application is measured (Y), (X−Y) × 100, the adhesion amount (g / m) 2 ) calculated.
塗布液を塗布した基材100cm2の質量を測定し(X)、次に塗布前の基材100cm2の質量を測定し(Y)、(X-Y)×100で付着量(g/m2)を算出した。 [Attached amount of resin layer]
The mass of the substrate 100 cm 2 coated with the coating solution is measured (X), and then the mass of the substrate 100 cm 2 before application is measured (Y), (X−Y) × 100, the adhesion amount (g / m) 2 ) calculated.
〔樹脂層に含まれる界面活性剤の定性・定量〕
樹脂層に含まれる界面活性剤の定性・定量は、LC/MS/MSを用い以下の手順で分析を行うことにより可能である。LC/MS/MSとはLC/MS(ガスクロマトグラフ質量分析計)では分析困難である界面活性剤のような不揮発性の化合物にも適用可能な質量分析手法である。 Qualitative and quantitative determination of surfactant contained in resin layer
Qualitative and quantitative determination of the surfactant contained in the resin layer can be performed by analysis using the LC / MS / MS according to the following procedure. 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).
樹脂層に含まれる界面活性剤の定性・定量は、LC/MS/MSを用い以下の手順で分析を行うことにより可能である。LC/MS/MSとはLC/MS(ガスクロマトグラフ質量分析計)では分析困難である界面活性剤のような不揮発性の化合物にも適用可能な質量分析手法である。 Qualitative and quantitative determination of surfactant contained in resin layer
Qualitative and quantitative determination of the surfactant contained in the resin layer can be performed by analysis using the LC / MS / MS according to the following procedure. 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).
<樹脂層に含まれる界面活性剤の溶液調製>
(1)カバーフィルムから樹脂層をそぎとり、そのうち0.04gを25mLメスフラスコに秤量する。
(2)メスフラスコにHFIP(1,1,1,1,3,3,3-ヘキサフルオロ-2-プロパノール)/クロロホルム(1/1)を1mL加えて樹脂層を溶解させる。
(3)クロロホルムを2mL加えた後に、アセトニトリルを徐々に加えてホットメルト接着剤成分を不溶化させる。
(4)アセトニトリルを加え25mLに定容後、調製した溶液をアセトニトリルで100倍希釈する。
(5)調製した100倍希釈液をPTFEディスクフィルター(0.45μm)でろ過して得られたろ液を測定溶液とする。 <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 μm) is used as a measurement solution.
(1)カバーフィルムから樹脂層をそぎとり、そのうち0.04gを25mLメスフラスコに秤量する。
(2)メスフラスコにHFIP(1,1,1,1,3,3,3-ヘキサフルオロ-2-プロパノール)/クロロホルム(1/1)を1mL加えて樹脂層を溶解させる。
(3)クロロホルムを2mL加えた後に、アセトニトリルを徐々に加えてホットメルト接着剤成分を不溶化させる。
(4)アセトニトリルを加え25mLに定容後、調製した溶液をアセトニトリルで100倍希釈する。
(5)調製した100倍希釈液をPTFEディスクフィルター(0.45μm)でろ過して得られたろ液を測定溶液とする。 <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 μm) is used as a measurement solution.
<樹脂層に含まれる界面活性剤の定性>
(6)手順(5)で得られた溶液をLC/MS/MSに供し、クロマトグラムから界面活性剤由来のピークが検出されるリテンションタイムおよびピーク面積を確認する。
(7)界面活性剤由来のピークについてMS分析を行うことで、界面活性剤由来の正イオンの式量を確認する。 <Characteristics of surfactant contained in resin layer>
(6) 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.
(6)手順(5)で得られた溶液をLC/MS/MSに供し、クロマトグラムから界面活性剤由来のピークが検出されるリテンションタイムおよびピーク面積を確認する。
(7)界面活性剤由来のピークについてMS分析を行うことで、界面活性剤由来の正イオンの式量を確認する。 <Characteristics of surfactant contained in resin layer>
(6) 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.
<標準溶液調製および検量線の作成>
(8)手順(6)および(7)にて定性済みの界面活性剤の標品(0.01g)を10mLメスフラスコに秤量後、メタノールで溶解して10mLに定容することで標準溶液とする。
(9)標準溶液を分取し、メタノールでそれぞれ希釈することで計4種類の任意の濃度の標準溶液を得る。
(10)手順(9)で得た標準溶液をそれぞれLC/MS/MSに供することで、各濃度に対するクロマトグラムのピーク面積を確認する。
(11)溶液濃度とピーク面積の関係について直線近似することで検量線を得る。 <Preparation of standard solution and preparation of calibration curve>
(8) Weigh the standard surfactant preparation (0.01 g) obtained in the procedures (6) and (7) into a 10 mL volumetric flask, dissolve it in methanol, and adjust to 10 mL with the standard solution. Do.
(9) Separate the standard solution and dilute each with methanol to obtain a total of four standard solutions of any concentration.
(10) Each of the standard solutions obtained in the procedure (9) is subjected to LC / MS / MS to confirm the peak area of the chromatogram for each concentration.
(11) A calibration curve is obtained by linear approximation of the relationship between the solution concentration and the peak area.
(8)手順(6)および(7)にて定性済みの界面活性剤の標品(0.01g)を10mLメスフラスコに秤量後、メタノールで溶解して10mLに定容することで標準溶液とする。
(9)標準溶液を分取し、メタノールでそれぞれ希釈することで計4種類の任意の濃度の標準溶液を得る。
(10)手順(9)で得た標準溶液をそれぞれLC/MS/MSに供することで、各濃度に対するクロマトグラムのピーク面積を確認する。
(11)溶液濃度とピーク面積の関係について直線近似することで検量線を得る。 <Preparation of standard solution and preparation of calibration curve>
(8) Weigh the standard surfactant preparation (0.01 g) obtained in the procedures (6) and (7) into a 10 mL volumetric flask, dissolve it in methanol, and adjust to 10 mL with the standard solution. Do.
(9) Separate the standard solution and dilute each with methanol to obtain a total of four standard solutions of any concentration.
(10) Each of the standard solutions obtained in the procedure (9) is subjected to LC / MS / MS to confirm the peak area of the chromatogram for each concentration.
(11) A calibration curve is obtained by linear approximation of the relationship between the solution concentration and the peak area.
<樹脂層に含まれる界面活性剤の定量>
(12)手順(6)にて把握したピーク面積を手順(11)で得た検量線の式に代入し、樹脂層に含まれる界面活性剤の濃度を算出することで界面活性剤の含有量を求める。 <Quantitation of surfactant contained in resin layer>
(12) The peak area obtained in step (6) is substituted into the equation of the calibration curve obtained in step (11), and the concentration of surfactant contained in the resin layer is calculated to calculate the content of surfactant Ask for
(12)手順(6)にて把握したピーク面積を手順(11)で得た検量線の式に代入し、樹脂層に含まれる界面活性剤の濃度を算出することで界面活性剤の含有量を求める。 <Quantitation of surfactant contained in resin layer>
(12) The peak area obtained in step (6) is substituted into the equation of the calibration curve obtained in step (11), and the concentration of surfactant contained in the resin layer is calculated to calculate the content of surfactant Ask for
なお、手順(1)~(7)および(11)、(12)については、n=2で実施し、その平均値を結果とする。
本分析は、LCシステム:LC-20A(株式会社島津製作所製)、MSシステム:API4000(株式会社AB SCIEX製)、カラム:Inertsil ODS-3(2.1×150mm、5μm)(ジーエルサイエンス株式会社製)を用い、カラム温度:50℃、流量:0.25mL/min、注入量:1μL、イオン化法:APCI(大気圧化学イオン化法)、検出:正イオン検出、測定モード:SRM(Selected reAction monitoring)の条件にて実施する。 The procedures (1) to (7) and (11) and (12) are carried out with n = 2, and the average value is taken as the result.
This analysis is performed using LC system: LC-20A (made by Shimadzu Corporation), MS system: API4000 (made by AB SCIEX Co., Ltd.), column: Inertsil ODS-3 (2.1 × 150 mm, 5 μm) (GL Sciences Inc.) Column temperature: 50 ° C., flow rate: 0.25 mL / min, injection amount: 1 μL, ionization method: APCI (atmospheric pressure chemical ionization method), detection: positive ion detection, measurement mode: SRM (Selected reAction monitoring) Conduct under the conditions of).
本分析は、LCシステム:LC-20A(株式会社島津製作所製)、MSシステム:API4000(株式会社AB SCIEX製)、カラム:Inertsil ODS-3(2.1×150mm、5μm)(ジーエルサイエンス株式会社製)を用い、カラム温度:50℃、流量:0.25mL/min、注入量:1μL、イオン化法:APCI(大気圧化学イオン化法)、検出:正イオン検出、測定モード:SRM(Selected reAction monitoring)の条件にて実施する。 The procedures (1) to (7) and (11) and (12) are carried out with n = 2, and the average value is taken as the result.
This analysis is performed using LC system: LC-20A (made by Shimadzu Corporation), MS system: API4000 (made by AB SCIEX Co., Ltd.), column: Inertsil ODS-3 (2.1 × 150 mm, 5 μm) (GL Sciences Inc.) Column temperature: 50 ° C., flow rate: 0.25 mL / min, injection amount: 1 μL, ionization method: APCI (atmospheric pressure chemical ionization method), detection: positive ion detection, measurement mode: SRM (Selected reAction monitoring) Conduct under the conditions of).
(実施例1)
ホットメルト接着剤を構成する樹脂として、融点100℃、数平均分子量22,000のポリエステル系接着剤樹脂をトルエンに溶解した20質量%溶液を用意し、さらにポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 レオドールTW-L106(HLB値:13.3)〕を用意し、固形分換算比が100質量部/4質量部の割合になるように塗布液を調合した。この塗布液をコンマコーターにてシリコーン系樹脂フィルムのシリコーン系樹脂塗布面に塗布し、120℃で30秒乾燥することで片面に付着量45g/m2の樹脂層1aを設けた後、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)に転写し、シリコーン系樹脂フィルムを剥離することでカバーフィルム1Aを得た。樹脂層1aの塗布厚さは20μmであった。 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. for 30 seconds to form a resin layer 1a with an adhesion amount of 45 g / m 2 on one side, and then Toray Co., Ltd. Transfer to a company-made polyethylene terephthalate (PET) film "Lumirror" (registered trademark) (type 100S28), and peeling off the silicone resin film to obtain a cover film 1A. The coating thickness of the resin layer 1a was 20 μm.
ホットメルト接着剤を構成する樹脂として、融点100℃、数平均分子量22,000のポリエステル系接着剤樹脂をトルエンに溶解した20質量%溶液を用意し、さらにポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 レオドールTW-L106(HLB値:13.3)〕を用意し、固形分換算比が100質量部/4質量部の割合になるように塗布液を調合した。この塗布液をコンマコーターにてシリコーン系樹脂フィルムのシリコーン系樹脂塗布面に塗布し、120℃で30秒乾燥することで片面に付着量45g/m2の樹脂層1aを設けた後、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)に転写し、シリコーン系樹脂フィルムを剥離することでカバーフィルム1Aを得た。樹脂層1aの塗布厚さは20μmであった。 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. for 30 seconds to form a resin layer 1a with an adhesion amount of 45 g / m 2 on one side, and then Toray Co., Ltd. Transfer to a company-made polyethylene terephthalate (PET) film "Lumirror" (registered trademark) (type 100S28), and peeling off the silicone resin film to obtain a cover film 1A. The coating thickness of the resin layer 1a was 20 μm.
次に、レーザー加工にて幅10mmの厚み方向に貫通した貫通孔(レーザー加工にて幅10mmの厚み方向に貫通した貫通孔とは、図2の符号1で示される基材Aのような形状で加工された部分をいう)を設けた東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100E20)に対し、カバーフィルム1Aの樹脂層面を合わせ、ヒートシーラーを用い前述の条件で貼合した。得られたサンプルの100E20面と、別に準備したもう一片のカバーフィルム1Aの樹脂層面を合わせ、再度ヒートシーラーを用い前述の条件で貼合することで本発明の積層体1を得た。積層体1は図1および2に対応する構成であり、この積層体1は本発明1の態様の構成を有するものである。
Next, 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. 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.
(実施例2)
実施例1において、一片の樹脂層1aを、ホットメルト接着剤を構成する樹脂として融点100℃、数平均分子量22,000のポリエステル系接着剤樹脂をトルエンに溶解した20質量%溶液を用意することで得られる樹脂層2bとする以外は同様にして本発明の積層体2を得た。積層体2は図1および2に対応する構成であり、この積層体2は本発明1の態様の構成を有するものである。 (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. Thelaminated 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.
実施例1において、一片の樹脂層1aを、ホットメルト接着剤を構成する樹脂として融点100℃、数平均分子量22,000のポリエステル系接着剤樹脂をトルエンに溶解した20質量%溶液を用意することで得られる樹脂層2bとする以外は同様にして本発明の積層体2を得た。積層体2は図1および2に対応する構成であり、この積層体2は本発明1の態様の構成を有するものである。 (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
(実施例3)
シリコーン系樹脂フィルムに樹脂層2bを設けた後、樹脂層2b面に東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100E20)を貼り合わせ、トムソン型を用いた打ち抜き手法にて幅10mmの厚み方向に貫通した貫通孔を設けた。その後、シリコーン系樹脂フィルムを剥離することでスペーサフィルム3を得た。得られたスペーサフィルム3の樹脂層2b面と東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)を、ヒートシーラーを用い実施例1の条件にて貼合した後、別途用意したカバーフィルム1Aの樹脂層1a面と、スペーサフィルム3のスペーサ基材を、実施例1の条件にてヒートシーラーを用い貼合することで本発明の積層体3を得た。積層体3は図3および4に対応する構成であり、この積層体3は本発明2の態様の構成を有するものである。 (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, thespacer 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. using a heat sealer under the conditions of Example 1 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.
シリコーン系樹脂フィルムに樹脂層2bを設けた後、樹脂層2b面に東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100E20)を貼り合わせ、トムソン型を用いた打ち抜き手法にて幅10mmの厚み方向に貫通した貫通孔を設けた。その後、シリコーン系樹脂フィルムを剥離することでスペーサフィルム3を得た。得られたスペーサフィルム3の樹脂層2b面と東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)を、ヒートシーラーを用い実施例1の条件にて貼合した後、別途用意したカバーフィルム1Aの樹脂層1a面と、スペーサフィルム3のスペーサ基材を、実施例1の条件にてヒートシーラーを用い貼合することで本発明の積層体3を得た。積層体3は図3および4に対応する構成であり、この積層体3は本発明2の態様の構成を有するものである。 (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
(実施例4)
実施例3において、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ188E20)の貼合面側にマグネトロンスパッタリング装置を用いて、厚さ10nmのパラジウム層をフィルム基材の一方の面上に形成したカバー材料4をスペーサフィルム3の樹脂層2b面に設ける以外は同様にして、本発明の積層体4を得た。なお、マグネトロンスパッタリングのターゲットには、純度99.9質量%のパラジウム(田中貴金属工業株式会社製)を用い、スパッタガスにはアルゴンを用いた。積層体4は図3および4に対応する構成であり、この積層体4は本発明2の態様の構成を有するものである。 (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 filmbase 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. In addition, as a target of magnetron sputtering, palladium with a purity of 99.9% by mass (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) was used, and argon was used as a sputtering gas. 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.
実施例3において、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ188E20)の貼合面側にマグネトロンスパッタリング装置を用いて、厚さ10nmのパラジウム層をフィルム基材の一方の面上に形成したカバー材料4をスペーサフィルム3の樹脂層2b面に設ける以外は同様にして、本発明の積層体4を得た。なお、マグネトロンスパッタリングのターゲットには、純度99.9質量%のパラジウム(田中貴金属工業株式会社製)を用い、スパッタガスにはアルゴンを用いた。積層体4は図3および4に対応する構成であり、この積層体4は本発明2の態様の構成を有するものである。 (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
(実施例5)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 レオドールTW-L106(HLB値:13.3)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体5を得た。積層体5は図3および4に対応する構成であり、この積層体5は本発明2の態様の構成を有するものである。 (Example 5)
In Example 4, 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. Alaminate 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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 レオドールTW-L106(HLB値:13.3)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体5を得た。積層体5は図3および4に対応する構成であり、この積層体5は本発明2の態様の構成を有するものである。 (Example 5)
In Example 4, 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
(実施例6)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体6を得た。積層体6は図3および4に対応する構成であり、この積層体6は本発明2の態様の構成を有するものである。 (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 Thelaminate 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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体6を得た。積層体6は図3および4に対応する構成であり、この積層体6は本発明2の態様の構成を有するものである。 (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
(実施例7)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比3質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体7を得た。積層体7は図3および4に対応する構成であり、この積層体7は本発明2の態様の構成を有するものである。 (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. Thelaminate 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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比3質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体7を得た。積層体7は図3および4に対応する構成であり、この積層体7は本発明2の態様の構成を有するものである。 (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
(実施例8)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比20質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体8を得た。積層体8は図3および4に対応する構成であり、この積層体8は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1508(HLB値:11.4)〕をホットメルト接着剤の固形分換算比20質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体8を得た。積層体8は図3および4に対応する構成であり、この積層体8は本発明2の態様の構成を有するものである。 (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
(実施例9)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1105-S(HLB値:10.5)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体9を得た。積層体9は図3および4に対応する構成であり、この積層体9は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1105-S(HLB値:10.5)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体9を得た。積層体9は図3および4に対応する構成であり、この積層体9は本発明2の態様の構成を有するものである。 (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
(実施例10)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1105-S(HLB値:10.5)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体10を得た。積層体10は図3および4に対応する構成であり、この積層体10は本発明2の態様の構成を有するものである。 (Example 10)
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 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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1105-S(HLB値:10.5)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体10を得た。積層体10は図3および4に対応する構成であり、この積層体10は本発明2の態様の構成を有するものである。 (Example 10)
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 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.
(実施例11)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 エマルゲン103(HLB値:8.1)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体11を得た。積層体11は図3および4に対応する構成であり、この積層体11は本発明2の態様の構成を有するものである。 (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 meltadhesive 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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 エマルゲン103(HLB値:8.1)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体11を得た。積層体11は図3および4に対応する構成であり、この積層体11は本発明2の態様の構成を有するものである。 (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
(実施例12)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 エマルゲン103(HLB値:8.1)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体12を得た。積層体12は図3および4に対応する構成であり、この積層体12は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔花王株式会社製 エマルゲン103(HLB値:8.1)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体12を得た。積層体12は図3および4に対応する構成であり、この積層体12は本発明2の態様の構成を有するものである。 (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
(実施例13)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 ニューカルゲンD-1205(HLB値:10.5)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体13を得た。積層体13は図3および4に対応する構成であり、この積層体13は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 ニューカルゲンD-1205(HLB値:10.5)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体13を得た。積層体13は図3および4に対応する構成であり、この積層体13は本発明2の態様の構成を有するものである。 (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
(実施例14)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 ニューカルゲンD-1205(HLB値:10.5)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体14を得た。積層体14は図3および4に対応する構成であり、この積層体14は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 ニューカルゲンD-1205(HLB値:10.5)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体14を得た。積層体14は図3および4に対応する構成であり、この積層体14は本発明2の態様の構成を有するものである。 (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
(実施例15)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 DTD-51(HLB値:13.7)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体15を得た。積層体15は図3および4に対応する構成であり、この積層体15は本発明2の態様の構成を有するものである。 (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 A laminate 15 of the present invention was obtained in the same manner as described above except that the coating solution was prepared. The laminate 15 has a configuration corresponding to FIGS. 3 and 4, and the laminate 15 has the configuration of the aspect of thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 DTD-51(HLB値:13.7)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体15を得た。積層体15は図3および4に対応する構成であり、この積層体15は本発明2の態様の構成を有するものである。 (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 A laminate 15 of the present invention was obtained in the same manner as described above except that the coating solution was prepared. The laminate 15 has a configuration corresponding to FIGS. 3 and 4, and the laminate 15 has the configuration of the aspect of the
(実施例16)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 DTD-51(HLB値:13.7)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体16を得た。積層体16は図3および4に対応する構成であり、この積層体16は本発明2の態様の構成を有するものである。 (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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 DTD-51(HLB値:13.7)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体16を得た。積層体16は図3および4に対応する構成であり、この積層体16は本発明2の態様の構成を有するものである。 (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.
(実施例17)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1007(HLB値:14.1)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体17を得た。積層体17は図3および4に対応する構成であり、この積層体17は本発明2の態様の構成を有するものである。 (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.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1007(HLB値:14.1)〕をホットメルト接着剤の固形分換算比4質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体17を得た。積層体17は図3および4に対応する構成であり、この積層体17は本発明2の態様の構成を有するものである。 (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.
(実施例18)
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1007(HLB値:14.1)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体18を得た。積層体18は図3および4に対応する構成であり、この積層体18は本発明2の態様の構成を有するものである。 (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 thepresent invention 2.
実施例4において、ポリアルキレングリコール骨格を有するノニオン界面活性剤〔竹本油脂株式会社製 パイオニンD-1007(HLB値:14.1)〕をホットメルト接着剤の固形分換算比8質量部の割合になるように塗布液を調合した以外は同様にして、本発明の積層体18を得た。積層体18は図3および4に対応する構成であり、この積層体18は本発明2の態様の構成を有するものである。 (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
(比較例1)
東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)上へ、ポリエステル樹脂100質量部に対してカチオン系界面活性剤(東邦化学工業(株)製 アンステックスC-200X)を、5質量部の割合で調合し、グラビアコータにて塗布し、親水コート層11を有するカバーフィルム19Aを得た。
次に、ポリエステル系接着剤樹脂をコンマコーターにてシリコーン系樹脂フィルムのシリコーン系樹脂塗布面に塗布しホットメルト樹脂層を設けた後、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100E20)に転写した。同様の手順でシリコーン系樹脂フィルムのシリコーン系樹脂塗布面にホットメルト樹脂層を設け、そこへ先の100E20のもう一方の面へホットメルト樹脂層を転写した。さらに、厚み方向に貫通した貫通孔を設けることでスペーサフィルム19Bを得た。
次に東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ188E20)の一方の面にマグネトロンスパッタリング装置を用いて、パラジウム層を形成した。
カバーフィルム19Aの親水コート面とスペーサフィルム19Bのホットメルト樹脂層面をヒートシーラーを用い前述の条件で貼合した。得られたサンプルのもう一方のホットメルト樹脂層面と、先のパラジウム面を合わせ、再度ヒートシーラーを用い前述の条件で貼合することで本発明の積層体19を得た。積層体19は図6に対応する親水コート層11を有する構成であり、請求項1および2で規定される積層体の構成を有さない。なお、図6は導入口と該導入口の反対側(すなわち、該導入口に対向する面)との間で積層体を厚み方向に切断し、導入口側から見た断面図である。
基材A、樹脂層Xおよび樹脂層Yのそれぞれの厚みを一定とした場合、図6に対応する比較例1に対し図3に対応する実施例1~18は、キャビティの高さを低く抑えることができるため液体試料の使用量を低減することができる。また、比較例1に対し実施例1~18は、親水コート層を設けていないため製造工程が簡略化される。 (Comparative example 1)
Cationic surfactant (Toho Chemical Industry Co., Ltd. Anstex C-200X) per 100 parts by mass of polyester resin onto polyethylene terephthalate (PET) film "Lumirror" (registered trademark) (type 100S28) manufactured by Toray Industries, Inc. Was prepared in a proportion of 5 parts by mass, and was coated by a gravure coater to obtain a cover film 19A having thehydrophilic coating layer 11.
Next, a polyester adhesive resin is applied to the silicone resin coated surface of the silicone resin film with a comma coater to form a hot melt resin layer, and then a polyethylene terephthalate (PET) film "Lumirror" manufactured by Toray Industries, Inc. (registration Transferred to trademark (type 100E20). 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. The other hot-melt resin layer surface of the obtained sample and the palladium surface described above were combined and bonded again using the heat sealer under the above-described conditions, to obtain a laminate 19 of the present invention. 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 | regulated by Claim 1 and 2. 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.
When the thickness of each of the base material A, the resin layer X and the resin layer Y is constant, Examples 1 to 18 corresponding to FIG. 3 keep the height of the cavity low compared to Comparative Example 1 corresponding to FIG. Therefore, the amount of liquid sample used can be reduced. Further, as compared with Comparative Example 1, in Examples 1 to 18, since the hydrophilic coat layer is not provided, the manufacturing process is simplified.
東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100S28)上へ、ポリエステル樹脂100質量部に対してカチオン系界面活性剤(東邦化学工業(株)製 アンステックスC-200X)を、5質量部の割合で調合し、グラビアコータにて塗布し、親水コート層11を有するカバーフィルム19Aを得た。
次に、ポリエステル系接着剤樹脂をコンマコーターにてシリコーン系樹脂フィルムのシリコーン系樹脂塗布面に塗布しホットメルト樹脂層を設けた後、東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ100E20)に転写した。同様の手順でシリコーン系樹脂フィルムのシリコーン系樹脂塗布面にホットメルト樹脂層を設け、そこへ先の100E20のもう一方の面へホットメルト樹脂層を転写した。さらに、厚み方向に貫通した貫通孔を設けることでスペーサフィルム19Bを得た。
次に東レ株式会社製ポリエチレンテレフタレート(PET)フィルム“ルミラー”(登録商標)(タイプ188E20)の一方の面にマグネトロンスパッタリング装置を用いて、パラジウム層を形成した。
カバーフィルム19Aの親水コート面とスペーサフィルム19Bのホットメルト樹脂層面をヒートシーラーを用い前述の条件で貼合した。得られたサンプルのもう一方のホットメルト樹脂層面と、先のパラジウム面を合わせ、再度ヒートシーラーを用い前述の条件で貼合することで本発明の積層体19を得た。積層体19は図6に対応する親水コート層11を有する構成であり、請求項1および2で規定される積層体の構成を有さない。なお、図6は導入口と該導入口の反対側(すなわち、該導入口に対向する面)との間で積層体を厚み方向に切断し、導入口側から見た断面図である。
基材A、樹脂層Xおよび樹脂層Yのそれぞれの厚みを一定とした場合、図6に対応する比較例1に対し図3に対応する実施例1~18は、キャビティの高さを低く抑えることができるため液体試料の使用量を低減することができる。また、比較例1に対し実施例1~18は、親水コート層を設けていないため製造工程が簡略化される。 (Comparative example 1)
Cationic surfactant (Toho Chemical Industry Co., Ltd. Anstex C-200X) per 100 parts by mass of polyester resin onto polyethylene terephthalate (PET) film "Lumirror" (registered trademark) (type 100S28) manufactured by Toray Industries, Inc. Was prepared in a proportion of 5 parts by mass, and was coated by a gravure coater to obtain a cover film 19A having the
Next, a polyester adhesive resin is applied to the silicone resin coated surface of the silicone resin film with a comma coater to form a hot melt resin layer, and then a polyethylene terephthalate (PET) film "Lumirror" manufactured by Toray Industries, Inc. (registration Transferred to trademark (type 100E20). 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. The other hot-melt resin layer surface of the obtained sample and the palladium surface described above were combined and bonded again using the heat sealer under the above-described conditions, to obtain a laminate 19 of the present invention. The laminated body 19 is a structure which has the hydrophilic-
When the thickness of each of the base material A, the resin layer X and the resin layer Y is constant, Examples 1 to 18 corresponding to FIG. 3 keep the height of the cavity low compared to Comparative Example 1 corresponding to FIG. Therefore, the amount of liquid sample used can be reduced. Further, as compared with Comparative Example 1, in Examples 1 to 18, since the hydrophilic coat layer is not provided, the manufacturing process is simplified.
本発明によれば、液体試料の使用量を低減すると共に製造工程が簡略化されたバイオセンサに好適な積層体を提供する。
According to the present invention, it is possible to provide a laminate suitable for a biosensor in which the amount of liquid sample used is reduced and the manufacturing process is simplified.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
本出願は、2017年10月20日出願の日本特許出願(特願2017-203166)に基づくものであり、その内容はここに参照として取り込まれる。 Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-203166) filed on October 20, 2017, the contents of which are incorporated herein by reference.
本出願は、2017年10月20日出願の日本特許出願(特願2017-203166)に基づくものであり、その内容はここに参照として取り込まれる。 Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-203166) filed on October 20, 2017, the contents of which are incorporated herein by reference.
1:基材A(スペーサ基材)
21:カバー材料B
22:カバー材料C
31:樹脂層X
32:樹脂層Y
4:キャビティ
41:導入口
5:カバーフィルム
6:積層体
7a:樹脂層Xで構成される面
7b:樹脂層Yで構成される面
8a、8b:基材Aのみで構成される面
9:カバー材料Cで構成される面
10a、10b:基材Aおよび樹脂層Yのみで構成される面
11:親水コート層
12a、12b:基材A、樹脂層Xおよび樹脂層Yで構成される面 1: Substrate A (Spacer substrate)
21: Cover material B
22: Cover material C
31: Resin layer X
32: Resin layer Y
4: Cavity 41: Inlet 5: Cover film 6:Laminate 7a: Surface 7b composed of resin layer X: Surface 8a composed of resin layer Y: Surface 9 composed only of base material A: 9 Surfaces 10a and 10b composed of the cover material C: Surfaces composed only of the base material A and the resin layer Y: Hydrophilic coated layers 12a and 12b: faces composed of the substrate A, resin layer X and resin layer Y
21:カバー材料B
22:カバー材料C
31:樹脂層X
32:樹脂層Y
4:キャビティ
41:導入口
5:カバーフィルム
6:積層体
7a:樹脂層Xで構成される面
7b:樹脂層Yで構成される面
8a、8b:基材Aのみで構成される面
9:カバー材料Cで構成される面
10a、10b:基材Aおよび樹脂層Yのみで構成される面
11:親水コート層
12a、12b:基材A、樹脂層Xおよび樹脂層Yで構成される面 1: Substrate A (Spacer substrate)
21: Cover material B
22: Cover material C
31: Resin layer X
32: Resin layer Y
4: Cavity 41: Inlet 5: Cover film 6:
Claims (7)
- カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(i)の面、(ii)の面および(iii)の面から構成されることを特徴とする積層体。
(i)樹脂層Xで構成される1面
(ii)樹脂層Yで構成される1面
(iii)基材Aのみで構成される3面 It 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, and the laminate has a cavity having an inlet port, A laminate comprising the surface of i), the surface of (ii) and the surface of (iii).
(I) One side composed of the resin layer X (ii) One side composed of the resin layer Y (iii) Three sides composed only of the base material A - カバー材料B、樹脂層X、基材A、樹脂層Yおよびカバー材料Cをこの順に有する積層体であって、前記積層体中に導入口を備えたキャビティを有し、該キャビティが以下の(iv)の面、(v)の面および(vi)の面から構成されることを特徴とする積層体。
(iv)樹脂層Xで構成される1面
(v)基材Aおよび樹脂層Yのみで構成される3面
(vi)カバー材料Cで構成される1面 It 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, and the laminate has a cavity having an inlet port, A laminate comprising the surface of iv), the surface of (v) and the surface of (vi).
(Iv) One Surface Composed of Resin Layer X (V) Three Surface Composed Only of Substrate A and Resin Layer Y (Vi) One Surface Constructed of Cover Material C - 前記樹脂層Xまたは樹脂層Yの少なくとも一方の樹脂層の表面の水接触角が15度未満である請求項1または2に記載の積層体。 The laminated body according to claim 1 or 2, wherein a water contact angle of a surface of at least one of the resin layer X and the resin layer Y is less than 15 degrees.
- 前記基材Aと樹脂層YとのJIS Z0237:2009に準拠した引きはがし角度90°の接着強度が、2.5N/10mm以上である請求項1~3のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the adhesive strength between the base material A and the resin layer Y in accordance with JIS Z0237: 2009 is at least 2.5 N / 10 mm. .
- 前記樹脂層Xおよび/または樹脂層Yに界面活性剤を含有する請求項1~4のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the resin layer X and / or the resin layer Y contains a surfactant.
- 前記樹脂層Xおよび/または樹脂層Yが、ポリエステル樹脂、(メタ)アクリル樹脂、ポリオレフィン樹脂、エチレン-酢酸ビニル共重合樹脂、ポリアミド樹脂、クロロプレン樹脂、アラミド樹脂およびアクリルウレタン樹脂からなる群より選ばれる少なくとも1つの樹脂を含有する請求項1~5のいずれか一項に記載の積層体。 The resin layer X and / or the resin layer Y is selected from the group consisting of polyester resin, (meth) acrylic resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, polyamide resin, chloroprene resin, aramid resin and acrylic urethane resin The laminate according to any one of claims 1 to 5, which contains at least one resin.
- 前記界面活性剤がポリアルキレングリコール骨格を有する非イオン性の界面活性剤である請求項5または6に記載の積層体。 The laminate according to claim 5 or 6, wherein the surfactant is a nonionic surfactant having a polyalkylene glycol skeleton.
Priority Applications (1)
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JP2018555792A JPWO2019078070A1 (en) | 2017-10-20 | 2018-10-10 | Laminate |
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JP2017-203166 | 2017-10-20 | ||
JP2017203166 | 2017-10-20 |
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Family
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PCT/JP2018/037824 WO2019078070A1 (en) | 2017-10-20 | 2018-10-10 | Laminate |
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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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006030160A (en) * | 2004-04-14 | 2006-02-02 | Hitachi Maxell Ltd | Reaction container |
JP2011185744A (en) * | 2010-03-09 | 2011-09-22 | Toray Ind Inc | Cover film used for biosensor |
WO2011125750A1 (en) * | 2010-03-31 | 2011-10-13 | シーシーアイ株式会社 | Biosensor |
JP2014215193A (en) * | 2013-04-26 | 2014-11-17 | 東洋インキScホールディングス株式会社 | Pressure sensitive adhesive sheet for liquid analytical member, and liquid analytical member |
JP2015182334A (en) * | 2014-03-25 | 2015-10-22 | 東レ株式会社 | Metal dot substrate, and method of manufacturing the same |
-
2018
- 2018-10-10 WO PCT/JP2018/037824 patent/WO2019078070A1/en active Application Filing
- 2018-10-10 JP JP2018555792A patent/JPWO2019078070A1/en active Pending
- 2018-10-16 TW TW107136255A patent/TW201922472A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006030160A (en) * | 2004-04-14 | 2006-02-02 | Hitachi Maxell Ltd | Reaction container |
JP2011185744A (en) * | 2010-03-09 | 2011-09-22 | Toray Ind Inc | Cover film used for biosensor |
WO2011125750A1 (en) * | 2010-03-31 | 2011-10-13 | シーシーアイ株式会社 | Biosensor |
JP2014215193A (en) * | 2013-04-26 | 2014-11-17 | 東洋インキScホールディングス株式会社 | Pressure sensitive adhesive sheet for liquid analytical member, and liquid analytical member |
JP2015182334A (en) * | 2014-03-25 | 2015-10-22 | 東レ株式会社 | Metal dot substrate, and method of manufacturing the same |
Cited By (1)
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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JPWO2019078070A1 (en) | 2020-09-17 |
TW201922472A (en) | 2019-06-16 |
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