JP7097196B2 - Laminates for biosensors and biosensors - Google Patents

Description

The present invention relates to a laminate and a biosensor for a biosensor, and more particularly to a laminate and a biosensor for a biosensor used for various purposes including those for medical use and sanitary materials.

Conventionally, a biological sensor that is attached to human skin or the like to detect a biological signal has been known.

As such biosensors, for example, in Patent Document 1, a viscous first layer, a second layer (polymer layer) arranged on the upper surface thereof, and a second layer (polymer layer) arranged on the lower surface of the second layer and in contact with the skin. Described is a biocompatible polymer substrate comprising electrodes to be used, a data acquisition module located on the upper surface of the first layer, and wiring arranged on the upper surface of the second layer to connect the electrodes and modules.

In the biocompatible polymer substrate described in Patent Document 1, the first layer is attached to human skin, the electrodes detect biological signals, for example, voltage signals derived from myocardium, and the data acquisition module is derived from myocardium. Receives and records voltage signals.

Japanese Unexamined Patent Publication No. 2012-10978

By the way, since the biosensor is used by being attached to human skin, depending on the place of attachment, the biosensor may be bent in the thickness direction or pulled in the surface direction according to the movement of the human skin. Occurs. As a result, there is a problem that the wiring is peeled off from the surface of the polymer layer.

Further, in order to facilitate the attachment of the biosensor to the skin, there is a usage mode in which the entire upper surface of the polymer substrate is covered with a support film (backing film) until immediately before use, and the support film is peeled off after the attachment. At this time, the wiring may be pulled by the support film due to the wiring being brought into close contact with the support film. As a result, there is a problem that the wiring is peeled off from the surface of the polymer layer.

These defects cause damage such as disconnection.

The present invention provides a laminate for a biosensor and a biosensor capable of suppressing the occurrence of peeling of a wiring layer.

In the present invention [1], a pressure-sensitive adhesive layer to be attached to a living body, a base material layer having elasticity arranged on the upper surface of the pressure-sensitive adhesive layer, and wiring embedded in the upper surface of the base material layer. The base material layer includes a layer for a biosensor, which comprises a layer and contains an amine-based silane coupling agent.

In the present invention [2], the base material layer contains the laminate for a biosensor according to [1], which contains a polyurethane resin.

The present invention [3] includes the laminate for a biosensor according to [2], wherein the amine-based silane coupling agent contains 0.1 part by mass or more with respect to 100 parts by mass of the polyurethane resin.

The present invention [4] includes the laminate for a biosensor according to any one of [1] to [3], wherein the amine-based silane coupling agent has a primary amine and a secondary amine. ..

The present invention [5] includes the laminate for a biosensor according to any one of [1] to [4], wherein the wiring layer is formed of copper wiring.

The present invention [6] is mounted on the base material layer so as to be electrically connected to the wiring layer with the biosensor laminate according to any one of [1] to [5]. Includes biosensors, including electronic components.

Since the laminate for biosensors and the biosensor of the present invention include a base material layer containing an amine-based silane coupling agent and a wiring layer arranged on the upper surface of the base material layer, the base material layer and the wiring layer are provided. Adhesion can be improved. As a result, peeling between the base material layer and the wiring layer can be suppressed.

FIG. 1 shows a plan view of an embodiment of the laminate for a biological sensor of the present invention. 2A and 2B are cross-sectional views of the biosensor laminate shown in FIG. 1, where FIG. 2A shows a cross-sectional view taken along line AA and FIG. 2B shows a cross-sectional view taken along line BB. 3A to 3D are manufacturing process diagrams of the laminate for a biosensor shown in FIG. 2A. FIG. 3A is a process of preparing a base material layer and a wiring layer, and FIG. 3B is a pressure-sensitive adhesive layer and a base material layer. 3C shows a step of forming an opening and preparing a probe member, FIG. 3D shows a step of fitting the probe member into the opening, and a step of forming a connecting portion. 4A and 4B are sectional views of a modified example (a form including a support film) of the laminated body for a biological sensor of the present invention, and FIG. 4A is a sectional view corresponding to the line AA of FIG. 1, FIG. 4B. Shows a cross-sectional view corresponding to line BB in FIG.

<One Embodiment>
The laminated body 1 for a biological sensor according to an embodiment of the present invention will be described with reference to FIGS. 1 to 3D.

In FIG. 1, the left-right direction of the paper surface is the longitudinal direction (first direction) of the biosensor laminate 1. The right side of the paper surface is one side in the longitudinal direction (one side in the first direction), and the left side of the paper surface is the other side in the longitudinal direction (the other side in the first direction).

In FIG. 1, the vertical direction of the paper surface is the lateral direction (direction orthogonal to the longitudinal direction, width direction, and second direction orthogonal to the first direction) of the laminate 1 for biosensors. The upper side of the paper surface is one side in the lateral direction (one side in the width direction, one side in the second direction), and the lower side of the paper surface is the other side in the lateral direction (the other side in the width direction, the other side in the second direction).

In FIG. 1, the paper thickness direction is the vertical direction (thickness direction, third direction orthogonal to the first direction and the second direction) of the biosensor laminate 1. The front side of the paper surface is the upper side (one side in the thickness direction, one side in the third direction), and the back side of the paper surface is the lower side (the other side in the thickness direction, the other side in the third direction). The direction conforms to the direction arrow shown in each drawing.

The definitions of these directions are not intended to limit the orientations of the biosensor laminate 1 and the patch-type electrocardiograph 30 (described later) during manufacturing and use.

As shown in FIGS. 1 to 2B, the biosensor laminate 1 has a substantially flat plate shape extending in the longitudinal direction. The biosensor laminate 1 includes a pressure-sensitive adhesive layer 2, a base material layer 3 arranged on the upper surface of the pressure-sensitive adhesive layer 2, a wiring layer 4 embedded in the base material layer 3, and a pressure-sensitive adhesive layer 2. A probe 5 embedded in the wiring layer 4 and a connecting portion 6 for electrically connecting the probe 5 are provided.

(Pressure-sensitive adhesive layer)
The pressure-sensitive adhesive layer 2 forms the lower surface of the biosensor laminate 1. The pressure-sensitive adhesive layer 2 is a layer that imparts pressure-sensitive adhesiveness to the lower surface of the biological sensor laminate 1 in order to attach the lower surface of the biological sensor laminate 1 to the biological surface (skin 33 or the like). .. The pressure-sensitive adhesive layer 2 forms the outer shape of the laminate 1 for a biosensor. The pressure-sensitive adhesive layer 2 has a flat plate shape (sheet shape) extending in the longitudinal direction. Specifically, for example, the pressure-sensitive adhesive layer 2 has a band shape extending in the longitudinal direction, and has a shape in which the central portion in the longitudinal direction bulges toward both outer sides in the lateral direction. Further, in the pressure-sensitive adhesive layer 2, the both end edges in the lateral direction of the central portion in the longitudinal direction are located on both outer sides in the lateral direction with respect to both end edges in the lateral direction other than the central portion in the longitudinal direction.

The pressure-sensitive adhesive layer 2 has adhesive openings 11 at both ends in the longitudinal direction thereof. Each of the two adhesive openings 11 has a substantially ring shape in a plan view and penetrates the pressure-sensitive adhesive layer 2 in the thickness direction. The adhesive opening 11 is filled with a connecting portion 6 (described later). Further, the lower surface inside the adhesive opening 11 has an adhesive groove 10 corresponding to the probe 5 (described later).

The material of the pressure-sensitive adhesive layer 2 is a material having pressure-sensitive adhesiveness, and preferably, a material further having biocompatibility can be mentioned. Examples of such a material include an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like, preferably an acrylic-based pressure-sensitive adhesive.

The acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive composition) contains an acrylic polymer.

The acrylic polymer is the main component of the acrylic pressure-sensitive adhesive and is a pressure-sensitive adhesive component.

As the acrylic polymer, for example, (meth) acrylic acid ester (specifically, isononyl acrylate, methoxyethyl acrylate, etc.) is used as a main component (content ratio in the monomer component is 70% by mass or more and 99% by mass or less). , Polymerizes a monomer component containing a monomer copolymerizable with (meth) acrylic acid ester (specifically, acrylic acid, etc.) as an optional component (content ratio in the monomer component is 30% by mass or less and 1% by mass or more). It is a polymer. Examples of the acrylic polymer include the acrylic polymer described in JP-A-2003-342541.

The acrylic pressure-sensitive adhesive preferably further contains a carboxylic acid ester.

The carboxylic acid ester in the acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive force adjusting agent that reduces the pressure-sensitive adhesive force of the acrylic polymer and adjusts the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 2. The carboxylic acid ester is a carboxylic acid ester that is compatible with the acrylic polymer.

Specifically, the same as the carboxylic acid ester in the base material composition described later in the base material layer 3 can be mentioned, and trifatty acid glyceryl is preferably mentioned.

The content ratio of the carboxylic acid ester is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, and for example, 100 parts by mass or less, preferably 70 parts by mass or less, based on 100 parts by mass of the acrylic polymer. Is.

Further, the acrylic pressure-sensitive adhesive may also contain a cross-linking agent, if necessary. The cross-linking agent is a cross-linking component that cross-links the acrylic polymer. Examples of the cross-linking agent include polyisocyanate compounds, epoxy compounds, melamine compounds, peroxide compounds, urea compounds, metal alkoxide compounds, metal chelate compounds, metal salt compounds, carbodiimide compounds, oxazoline compounds, aziridine compounds, amine compounds and the like. Be done. These cross-linking agents can be used alone or in combination. The cross-linking agent is preferably a polyisocyanate compound (polyfunctional isocyanate compound).

The content ratio of the cross-linking agent is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and for example, 10 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the acrylic polymer. It is less than the mass part.

The thickness of the pressure-sensitive adhesive layer 2 (excluding the region of the adhesive groove 10) is, for example, 10 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 100 μm or less, more preferably. It is 50 μm or less.

(Base layer)
As shown in FIG. 1, the base material layer 3 forms the upper surface of the biosensor laminate 1. The base material layer 3 and the pressure-sensitive adhesive layer 2 form the outer shape of the laminate 1 for a biosensor. The plan view shape of the base material layer 3 is the same as the plan view shape of the pressure-sensitive adhesive layer 2. The base material layer 3 is arranged on the entire upper surface of the pressure-sensitive adhesive layer 2. The base material layer 3 is a support layer that supports the pressure-sensitive adhesive layer 2. The base material layer 3 has a sheet shape extending in the longitudinal direction.

As shown in FIGS. 2A to 2B, a base material groove 14 corresponding to the wiring layer 4 is formed on the upper surface of the base material layer 3. The base material groove 14 has the same pattern shape as the wiring layer 4 in a plan view. The base material groove 14 is opened upward.

Further, the base material layer 3 has a base material opening 15 corresponding to the adhesive opening 11. The base material opening 15 communicates with the adhesive opening 11 in the thickness direction. The base material opening 15 has a substantially ring shape in a plan view having the same shape and dimensions as the adhesive opening 11.

The elongation at break of the base material layer 3 is, for example, 100% or more, preferably 200% or more, more preferably 300% or more, and for example, 2000% or less. The elongation at break is measured with a test piece type 2 at a tensile speed of 5 mm / min according to JIS K 7127 (1999).

The tensile strength of the base material layer 3 at 20 ° C. (chuck spacing 100 mm, tensile speed 300 mm / min, strength at break) is, for example, 0.1 N / 20 mm or more, preferably 1 N / 20 mm or more, and also. For example, it is 20 N / 20 mm or less. Tensile strength is measured based on JIS K 7127 (1999).

Further, the tensile storage elastic modulus E'at 20 ° C. of the base material layer 3 is, for example, 2,000 MPa or less, preferably 1,000 MPa or less, more preferably 100 MPa or less, still more preferably 50 MPa or less, and particularly preferably 50 MPa or less. , 20 MPa or less, and for example, 0.1 MPa or more. The tensile storage elastic modulus E'at 20 ° C. is determined by dynamic viscoelasticity measurement of the substrate layer 3 under the conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min.

Then, at least one of the following requirements, that is, (1) elongation at break of 100% or more, (2) tensile strength of 20 N / 20 mm or less, and (3) tensile storage elastic modulus E'of 2,000 MPa or less, preferably 2. The material of the substrate layer 3 is elastic if one or more requirements, more preferably all three requirements are met.

The peel strength (peeling strength) of the base material layer 3 with respect to the copper foil is, for example, 0.5 N / cm or more, preferably 1.0 N / cm or more, more preferably 2.0 N / cm or more, still more preferably. It is 2.5 N / cm or more. When the peel strength is equal to or higher than the above lower limit, the peeling between the base material layer 3 and the wiring layer 4 can be suppressed more reliably. The peel strength of the base material layer 3 is, for example, for a sample having a width of 1 cm (a laminate of the base material layer 3 and a copper foil) under the conditions of a peeling angle of 180 degrees and a peeling speed of 30 mm / min using a tensile tester. Is measured by peeling from the copper foil.

The base material layer 3 is formed from the base material composition. The base material composition contains a base material resin and an amine-based silane coupling agent.

The base material resin is a main component in the base material composition, and is, for example, a flexible resin capable of imparting appropriate elasticity, flexibility, and toughness to the base material layer 3.

Examples of the base resin include thermoplastic resins such as polyurethane resin, silicone resin, polystyrene resin, vinyl chloride resin, and polyester resin. Polyurethane resin is preferable. Thereby, the base material layer 3 can secure more excellent elasticity. Further, the adhesion with the wiring layer 4 can be surely improved by the interaction or compatibility with the amine-based coupling agent.

The polyurethane resin is, for example, a polymer of isocyanate and a polyol.

Examples of the isocyanate include diisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene diisocyanate, and norbornene diisocyanate. Preferred is diphenylmethane diisocyanate.

Examples of the polyol include polyether glycol, polyether polyol, polyester polyol, polymer polyol and the like. Preferred are polyether glycols.

Examples of the polyether glycol include polytetramethylene ether glycol and a copolymer of tetrahydrofuran and neopentyl glycol. Preferred are polytetramethylene ether glycols.

The molar ratio of isocyanate to polyol is, for example, isocyanate: polyol = 1:99 to 50:50, preferably 2:98 to 30:70, more preferably 3:97 to 9:91. When the molar ratio is in the above range, the adhesion between the wiring layer 4 and the base material layer 3 can be further improved.

The content ratio of the base resin in the base composition (base layer 3) is, for example, 70% by mass or more, preferably 80% by mass or more, and for example, 99% by mass or less, preferably 95% by mass. % Or less.

The amine-based silane coupling agent is a compound having both an amine and a hydrolyzable silyl group.

The amine may be, for example, any of a primary amine (amino group (-NH ₂ )), a secondary amine (-NH-), and a tertiary amine (-N =). A primary amine is preferred, and a combination of a primary amine and a secondary amine is more preferred.

Examples of the hydrolyzable silyl group include a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group, and a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Preferably, from the viewpoint of reactivity, a trialkoxysilyl group is mentioned, and more preferably, a trimethoxysilyl group is mentioned.

Specifically, examples of the amine-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and the like. 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like can be mentioned. These amine-based silane coupling agents can be used alone or in combination.

Preferred examples thereof include amino silane coupling agents having both primary and secondary amines, and specific examples thereof include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2. -(Aminoethyl) -3-aminopropyltrimethoxysilane can be mentioned. By using this amino silane coupling agent, the adhesion between the base material layer 3 and the wiring layer 4 can be further improved.

The content ratio of the amine-based coupling agent to 100 parts by mass of the base resin is, for example, 0.1 part by mass or more, preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, and also. For example, it is 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8.0 parts by mass or less. The content ratio of the amine-based coupling agent in the base material composition (base material layer 3) is, for example, 0.3% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more. For example, it is 30% by mass or less, preferably 25% by mass or less, and more preferably 15% by mass or less. When the content ratio of the amine-based coupling agent is within the above range, the adhesion between the base material layer 3 and the wiring layer 4 can be further improved.

The substrate composition preferably further contains a carboxylic acid ester. The carboxylic acid ester in the base material composition is an elastic adjusting agent for imparting flexibility to the laminate 1 for a biosensor.

The carboxylic acid ester is, for example, an ester of a carboxylic acid and an alcohol.

Examples of the carboxylic acid include fatty acids containing one carboxyl group in the molecule. Examples of fatty acids include linear saturated fatty acids such as valeric acid, caproic acid, ethanoic acid, capric acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid. For example, branched saturated fatty acids such as 2-ethylhexanoic acid, dimethyloctanoic acid and isostearic acid, and monocarboxylic acids such as unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid can be mentioned.

Further, examples of the carboxylic acid include polyvalent carboxylic acids containing two or more carboxyl groups in the molecule, such as dicarboxylic acids such as fumaric acid and phthalic acid. Further, examples of the carboxylic acid include hydroxycarboxylic acids such as lactic acid.

Examples of the carboxylic acid include fatty acids containing one carboxyl group in the molecule, more preferably linear saturated fatty acids, and further preferably linear saturated fatty acids having 6 or more and 18 or less carbon atoms. However, caprylic acid (8 carbon atoms) is particularly preferable.

Examples of the alcohol include monohydric alcohol and polyhydric alcohol.

Examples of the monohydric alcohol include methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, decanol, cetyl alcohol, isocetyl alcohol, myristyl alcohol, stearyl alcohol and the like.

Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol and diglycerin.

Examples of the alcohol include polyhydric alcohols, more preferably trihydric alcohols, and even more preferably glycerin.

Specifically, examples of the carboxylic acid ester include glyceryl tricaprylate, glyceryl monocaprylate, glyceryl tri-2-ethylhexanate, glyceryl tricaprate, glyceryl trilaurate, glyceryl triisostearate, glyceryl trioleate, and tri. Examples thereof include an ester of a carboxylic acid (fatty acid) and a trivalent alcohol, such as -2-ethylhexanoic acid trimethylolpropane. Examples of the carboxylic acid ester include esters of a carboxylic acid and a dihydric alcohol such as propylene glycol dicaprylate, propylene glycol dicaprate, and propylene glycol diisostearate. Examples of the carboxylic acid ester include ethyl myristate, isopropyl myristate, isopropyl palmitate, butyl stearate, isopropyl isostearate, hexyl laurate, diethyl phthalate, dioctyl phthalate, stearyl myristate, and stearyl oleate. Examples thereof include esters of a carboxylic acid and a monovalent alcohol such as cetyl dimethyloctanoate, cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate and dioctyl succinate. Further, examples of the carboxylic acid ester include cetyl lactate and myristyl lactate. These carboxylic acid esters can be used alone or in combination.

The carboxylic acid ester is preferably an ester of a fatty acid and a trivalent alcohol, more preferably an ester of a fatty acid and glycerin from the viewpoint of compatibility, and further preferably a linear saturation. Esters of fatty acids and glycerin, particularly preferably glyceryl tricaprylate, are mentioned.

The content ratio of the carboxylic acid ester to 100 parts by mass of the base resin is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, and for example, 80 parts by mass or less, preferably 70 parts by mass or less. .. The content ratio of the carboxylic acid ester in the base material composition (base material layer 3) is, for example, 10% by mass or more, preferably 25% by mass or more, and for example, 45% by mass or less, preferably 35% by mass. % Or less.

The thickness of the base material layer 3 (excluding the region of the base material groove 14) is, for example, 1 μm or more, preferably 5 μm or more, and for example, 300 μm or less, preferably 100 μm or less, preferably 50 μm. It is as follows. When the thickness of the base material layer 3 is at least the above lower limit, the base material layer 3 can be reliably held in shape, so that the handleability of the biosensor laminate 1 is excellent. When the thickness of the base material layer 3 is not more than the above upper limit, the base material layer 3 can be reliably attached to the living body.

(Wiring layer)
As shown in FIGS. 2A to 2B, the wiring layer 4 is embedded in the base material groove 14 of the base material layer 3. Specifically, the wiring layer 4 is embedded in the upper end portion of the base material layer 3 so as to be exposed from the upper surface of the base material layer 3. All of the lower surface and all of the side surfaces of the wiring layer 4 are in contact with the base material layer 3. The upper surface of the wiring layer 4 is exposed from the upper surface of the base material layer 3. The upper surface of the wiring layer 4 forms the upper surface of the biosensor laminate 1 together with the upper surface of the base material layer 3, and the upper surface of the wiring layer 4 is flush with the upper surface of the base material layer 3.

As shown in FIG. 1, the wiring layer 4 has a wiring pattern for connecting the connection portion 6, the electronic component 31 (described later), and the battery 32 (described later). Specifically, the wiring layer 4 independently includes the first wiring pattern 41 and the second wiring pattern 42.

The first wiring pattern 41 is arranged on one side in the longitudinal direction of the base material layer 3. The first wiring pattern 41 includes a first wiring 16A, and a first terminal 17A and a second terminal 17B continuous with the first wiring 16A.

The first wiring pattern 41 has a substantially T-shape in a plan view. Specifically, the first wiring pattern 41 extends from one end in the longitudinal direction of the base material layer 3 toward the other side in the longitudinal direction, branches at the central portion in the longitudinal direction of the base material layer 3, and faces both outer sides in the lateral direction. Extend.

Each of the first terminal 17A and the second terminal 17B is arranged at both ends in the lateral direction in the central portion in the longitudinal direction of the base material layer 3. Each of the first terminal 17A and the second terminal 17B has a substantially rectangular shape (land shape) in a plan view. Each of the first terminal 17A and the second terminal 17B is continuous with both ends of the first wiring 16A extending outward on both sides in the lateral direction in the central portion in the longitudinal direction of the base material layer 3.

The second wiring pattern 42 is provided on the other side in the longitudinal direction of the first wiring pattern 41 at intervals. The second wiring pattern 42 includes a second wiring 16B, and a third terminal 17C and a fourth terminal 17D that are continuous with the second wiring 16B.

The second wiring pattern 42 has a substantially T-shape in a plan view. Specifically, the second wiring pattern 42 extends from the other end in the longitudinal direction of the base material layer 3 toward one side in the longitudinal direction, branches at the central portion in the longitudinal direction of the base material layer 3, and extends to both outer sides in the lateral direction. Extend towards.

Each of the third terminal 17C and the fourth terminal 17D is arranged at both ends in the lateral direction in the central portion in the longitudinal direction of the base material layer 3. Each of the third terminal 17C and the fourth terminal 17D has a substantially rectangular shape (land shape) in a plan view. Each of the third terminal 17C and the fourth terminal 17D is continuous with both ends of the second wiring 16B extending outward on both sides in the lateral direction in the central portion in the longitudinal direction of the base material layer 3.

Examples of the material of the wiring layer 4 include conductors such as copper, nickel, gold, and alloys thereof. The wiring layer 4 preferably includes copper wiring made of copper.

The thickness of the wiring layer 4 is, for example, 0.1 μm or more, preferably 1 μm or more, and for example, less than 100 μm, preferably 50 μm or less, and more preferably 5 μm or less.

(probe)
The probe 5 is an electrode that, when the pressure-sensitive adhesive layer 2 is attached to the surface of a living body, comes into contact with the surface of the living body and senses an electric signal, temperature, vibration, sweat, metabolites, etc. from the living body.

As shown in FIGS. 2A to 2B, the probe 5 is embedded in the adhesive groove 10 of the pressure-sensitive adhesive layer 2. Specifically, the probe 5 is embedded in the lower end portion of the pressure-sensitive adhesive layer 2 inside the adhesive opening 11. The probe 5 has a substantially grid-like shape (or a substantially mesh shape) in a plan view. The lower surface of the probe 5 is exposed from the lower surface of the pressure-sensitive adhesive layer 2.

Examples of the material of the probe 5 include the material (specifically, the conductor) exemplified in the wiring layer 4.

The thickness of the probe 5 is, for example, 0.1 μm or more, preferably 1 μm or more, and for example, less than 100 μm, preferably 50 μm or less, more preferably 10 μm or less.

(Connection part)
As shown in FIGS. 2A to 2B, the connecting portion 6 is provided corresponding to the base material opening 15 and the adhesive opening 11, and has the same shape as them. The connecting portion 6 penetrates (passes) the base material layer 3 and the pressure-sensitive adhesive layer 2 in the thickness direction (vertical direction), and fills the base material opening 15 and the adhesive opening 11. The connecting portion 6 has a substantially cylindrical shape in which the axis extends in the thickness direction.

The inner surface of the connecting portion 6 is in contact with the probe 5, the pressure-sensitive adhesive layer 2 inside the adhesive opening 10, and the substrate layer 3 inside the substrate opening 15. The outer surface of the connection portion 6 is formed on the wiring layer 4 (first wiring 16A, second wiring 16B), the pressure-sensitive adhesive layer 2 outside the adhesive opening 10, and the base material layer 3 outside the base material opening 15. Are in contact. As a result, the connecting portion 6 electrically connects the wiring layer 4 and the probe 5.

Examples of the material of the connecting portion 6 include metals, conductive resins (including conductive polymers), and preferably conductive resins.

(Production method)
Next, an embodiment of a method for manufacturing the laminated body 1 for a biological sensor will be described.

As shown in FIG. 3A, in this method, first, the base material layer 3 and the wiring layer 4 are prepared.

For example, the base material layer 3 and the wiring layer 4 so that the wiring layer 4 is embedded in the base material groove 14 in accordance with the methods described in JP-A-2017-22236 and JP-A-2017-22237. Prepare. For the preparation of the base material layer 3, a base material composition containing the above-mentioned base material resin and an amine coupling agent is used.

As shown in FIG. 3B, the pressure-sensitive adhesive layer 2 is then arranged on the lower surface of the base material layer 3.

To arrange the pressure-sensitive adhesive layer 2, for example, first, a coating liquid containing the material of the pressure-sensitive adhesive layer 2 (for example, the acrylic pressure-sensitive adhesive described above) is prepared, and then the coating liquid is peeled off. It is applied to the upper surface of the sheet 19 and then dried by heating. As a result, the pressure-sensitive adhesive layer 2 is arranged on the upper surface of the release sheet 19. The release sheet 19 has, for example, a sheet shape extending in the longitudinal direction. Examples of the material of the release sheet 19 include a resin such as polyethylene terephthalate.

Next, the pressure-sensitive adhesive layer 2 and the base material layer 3 are bonded together by, for example, a laminator or the like. Specifically, the upper surface of the pressure-sensitive adhesive layer 2 and the lower surface of the base material layer 3 are brought into contact with each other.

At this point, each of the pressure-sensitive adhesive layer 2 and the base material layer 3 does not have the adhesive opening 11 and the base material opening 15.

As shown in FIG. 3C, the laminated opening 20 is then formed in the pressure-sensitive adhesive layer 2 and the base material layer 3.

The laminated opening 20 penetrates the laminated body of the pressure-sensitive adhesive layer 2 and the base material layer 3. The laminated opening 20 is a hole (through hole) having a substantially circular shape in a plan view, which is partitioned by an outer peripheral surface for partitioning the adhesive opening 11 and an outer peripheral surface for partitioning the base material opening 15. The laminated opening 20 is opened upward. On the other hand, the lower end of the laminated opening 20 is closed by the release sheet 19.

To form the laminated opening 20, the pressure-sensitive adhesive layer 2 and the base material layer 3 are punched or half-etched, for example.

Next, the probe member 18 is prepared and fitted into the laminated opening 20.

The probe member 18 has a substantially circular shape in a plan view. The probe member 18 includes a probe 5, a pressure-sensitive adhesive layer 2 in which the probe 5 is embedded, and a base material layer 3 arranged on the upper surface of the pressure-sensitive adhesive layer 2.

To prepare the probe member 18, a probe-containing sheet is prepared, and the probe-containing sheet is externally processed by punching or the like. As the probe-containing sheet, for example, a pressure-sensitive adhesive layer 2 and a probe 1 embedded in the lower surface thereof are manufactured in accordance with the methods described in JP-A-2017-22236 and JP-A-2017-22237. Then, it is prepared by laminating the base material layer 3 on the upper surface of the pressure-sensitive adhesive layer 2.

Then, as shown by the arrow in FIG. 3C, the probe member 18 is fitted into the laminated opening 20.

At this time, a space is provided between the pressure-sensitive adhesive layer 2, the base material layer 3 and the probe 5 of the probe member 18, and the pressure-sensitive adhesive layer 2 and the base material layer 3 around the laminated opening 20. That is, the probe member 18 is fitted into the laminated opening 20 so that the base material opening 15 and the adhesive opening 11 are formed.

Then, as shown in FIG. 3D, the connecting portion 6 is provided in the base material opening 15 and the adhesive opening 11.

When the material of the connecting portion 6 is a conductive resin composition, the conductive resin composition is injected into the base material opening 15 and the adhesive opening 11. Then, if necessary, the conductive resin composition is heated.

As a result, the laminated body 1 for a biological sensor is obtained.

The biosensor laminate 1 thus obtained includes a pressure-sensitive adhesive layer 2, a base material layer 3, a wiring layer 4, a probe 5, a connection portion 6, and a release sheet 19. As shown in FIGS. 2A and 2B, the biosensor laminate 1 does not include the release sheet 19, and is connected to the pressure-sensitive adhesive layer 2, the base material layer 3, the wiring layer 4, and the probe 5. It may consist only of part 6.

The biosensor laminate 1 includes a base material layer 3 containing an amine-based silane coupling agent, and a wiring layer 4 arranged on the upper surface of the base material layer 3. Therefore, the adhesion between the base material layer 3 and the wiring layer 4 is improved. Therefore, when the laminate 1 for a biological sensor is attached to the skin 33 of a living body, even if it is bent in the thickness direction or pulled in the plane direction, the peeling of the base material layer 3 and the wiring layer 4 is suppressed. be able to.

Further, the wiring layer 4 is embedded in the upper surface of the base material layer 3. Therefore, the contact area between the base material layer 3 and the wiring layer 4 is increased, and the adhesion between the base material layer 3 and the wiring layer 4 is further improved. Further, the base material layer 3 can protect the wiring layer 4 against an impact from the outside from the surface direction.

Therefore, when the laminated body 1 for a biological sensor is attached to the skin 33 of a living body, it is possible to suppress the occurrence of disconnection.

In particular, when the base resin is a polyurethane resin, the adhesion to the wiring layer 4 (particularly, copper wiring) can be more reliably improved from the viewpoint of interaction or compatibility with the amino-based coupling agent. ..

The biosensor laminate 1 is a device that is distributed independently and can be industrially used. Specifically, the biosensor laminate 1 can be distributed independently of the electronic component 31 and the battery 32 (see the virtual line in FIG. 1) described below. That is, the laminate 1 for a biosensor does not have the electronic component 31 and the battery 32 mounted therein, and is a component for manufacturing a biosensor such as a stick-on electrocardiograph 30.

(Biological sensor)
Next, as an example of the biosensor, a sticking type electrocardiograph 30 including the laminate 1 for the biosensor will be described.

As shown in FIGS. 1 and 2A to 2B, in order to manufacture the patch type electrocardiograph 30, for example, first, for example, each of the biosensor laminate 1, the electronic component 31 and the battery 32 is prepared.

The electronic component 31 includes, for example, an analog front end for processing and storing an electric signal from a living body acquired by the probe 5, a microcomputer, a memory, and further, the electric signal is converted into a radio wave and received externally. Examples include a communication IC for wirelessly transmitting to a machine, a transmitter, and the like. The electronic component 31 may have a part or all of them. The electronic component 31 has two or three or more terminals (not shown) provided on the lower surface thereof.

The battery 32 has two terminals (not shown) provided on its lower surface.

Next, the two terminals of the electronic component 31 are electrically connected to the first terminal 17A and the third terminal 17C. Further, the two terminals of the battery 32 are electrically connected to the second terminal 17B and the fourth terminal 17D.

As a result, a stick-on electrocardiograph 30 including a laminate 1 for a biosensor and an electronic component 31 and a battery 32 mounted therein is obtained.

To use the patch-type electrocardiograph 30, first, the release sheet 19 (see the arrow and the virtual line in FIG. 3D) is peeled from the pressure-sensitive adhesive layer 2 and the probe 5.

As shown by the virtual line in FIG. 2A, the lower surface of the pressure-sensitive adhesive layer 2 is then brought into contact with, for example, the skin 33 of the human body. Specifically, the pressure-sensitive adhesive layer 2 is pressure-sensitively adhered (attached) to the surface of the skin 33. As a result, the lower surface of the probe 5 also comes into contact with the surface of the skin 33.

Subsequently, the probe 5 senses the action potential of the heart as an electric signal, and the electric signal sensed by the probe 5 is input to the electronic component 31 via the connection portion 6 and the wiring layer 4. The electronic component 31 processes an electric signal and stores it as information based on the electric power supplied from the battery 32. Further, if necessary, the electric signal is converted into a radio wave and wirelessly transmitted to an external receiver.

Since the stick-on electrocardiograph 30 includes the laminate 1 for a biosensor, the adhesion between the base material layer 3 and the wiring layer 4 is improved. Therefore, even when the wiring layer 4 is attached to the skin 33 of a living body and used for a long time, it is possible to suppress the disconnection of the wiring layer 4 and the durability is excellent.

<Modification example>
In each of the following modifications, the same members and processes as those in the above-described embodiment are designated by the same reference numerals, and detailed description thereof will be omitted. In addition, each modification can be combined as appropriate. Further, each modification can exhibit the same effect as that of one embodiment, except for special mention.

(First modification)
In the above-mentioned stick-on electrocardiograph 30, the upper surface of the base material layer 3 is exposed. For example, as shown in FIG. 4, the stick-on electrocardiograph 30 is arranged on the upper surface of the base material layer 3. The support film 40 can be provided.

The support film 40 protects the electronic component 31 and the battery 32 before the attachment type electrocardiograph 30 is attached, and at the time of attachment, imparts appropriate mechanical strength to the attachment type electrocardiograph 30 to give the attachment type heart. The electric meter 30 is easily attached to the skin 33, and is peeled off from the attached electrocardiograph 30 when the attached electrocardiograph 30 is used.

The support film 40 is arranged on the upper surfaces of the base material layer 3, the wiring layer 4, the electronic component 31, and the battery 32. Specifically, the support film 40 is arranged on the upper surface of the base material layer 3, the upper surface of the wiring layer 4, the upper surface and the side surface of the electronic component 31, and the upper surface and the side surface of the battery 32 so as to cover them. There is. The support film 40 has a sheet shape extending in the longitudinal direction.

Examples of the support film 40 include a polyethylene terephthalate (PET) film, a polyvinyl chloride film, a resin film such as a polyethylene film, and the like.

The lower surface of the support film 40 preferably has adhesiveness.

The adhesive strength (peeling strength) of the support film 40 to the substrate layer 3 is, for example, 0.01 N / 20 mm or more, preferably 0.1 N / 20 mm or more, and for example, 6.0 N / 20 mm or less, preferably 6.0 N / 20 mm or less. Is 3.0 N / 20 mm or less. The adhesive strength is measured, for example, by supporting a sample having a width of 20 mm (a laminate of the base material layer 3 and the support film 40) under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min using a tensile tester. It is measured by peeling off the film 40.

The thickness of the support film 40 is, for example, 10 μm or more, preferably 50 μm or more, and for example, 1000 μm or less, preferably 500 μm or less.

In this sticking type electrocardiograph 30, the adhesion between the base material layer 3 and the wiring layer 4 is excellent. Therefore, even when the support film 40 is peeled off from the base material layer 3 and the wiring layer 4 when the stick-on electrocardiograph 30 is used, the wiring layer 4 is difficult to peel off from the base material layer 3. Therefore, the disconnection of the wiring layer 4 can be suppressed.

(Second modification)
In the above embodiment, as shown in FIGS. 2A to 2B, all the side surfaces of the wiring layer 4 are in contact with the base material layer 3, but for example, although not shown, the lower portion of the side surface of the wiring layer 4 is not shown. It comes into contact with the base material layer 3 and the upper portion of the side surface of the wiring layer 4 can be exposed from the upper surface of the base material layer 3. That is, the upper part of the wiring layer 4 protrudes from the upper surface of the base material layer 3, and the lower part of the wiring layer 4 is embedded in the base material layer 3.

Preferably, from the viewpoint of the adhesion between the base material layer 3 and the wiring layer 4, one embodiment shown in FIGS. 2A to 2B can be mentioned.

(Third modification example)
In one embodiment shown in FIGS. 1 and 2A to 2B, a patch-type electromyogram 30 is given as an example of the biological sensor of the present invention. Examples include devices that can be monitored, and specific examples thereof include a patch-type electroencephalograph, a patch-type sphygmomanometer, a patch-type pulse rate monitor, a patch-type electromyogram, and a patch-type thermometer.

The living body includes a human body and an animal other than the human body, but is preferably a human body.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to Examples and Comparative Examples. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios corresponding to them described in the above-mentioned "form for carrying out the invention" (forms for carrying out the invention). It can be replaced with the upper limit (value defined as "less than or equal to" or "less than") or the lower limit (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. can.
do.

<Preparation of substrate composition>
(Example 1)
Polyurethane-containing solution (containing 20% by mass of polyurethane A, which will be described later, methyl ethyl ketone (solvent): 40% by mass, dimethylformamide (solvent): 40% by mass) and glyceryl tricaprylate (trade name "Coconade", manufactured by Kao). And a silane coupling agent (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, trade name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd.), polyurethane: glyceryl tricaprylate: silane coupling agent. A base composition solution was prepared by mixing and stirring so that the mass ratio (solid content) of the above was 100: 10: 0.1.

(Examples 2 to 10)
A base composition solution was prepared in the same manner as in Example 1 except that the types and formulations of the polyurethane and silane coupling agents were changed to the types and formulations shown in Table 1.

(Comparative Examples 1 to 6)
A base composition solution was prepared in the same manner as in Example 1 except that the types and formulations of the polyurethane and silane coupling agents were changed to the types and formulations shown in Table 1.

<Preparation of pressure-sensitive adhesive composition>
An acrylic polymer was prepared by copolymerizing 65 parts by mass of isononyl acrylate, 30 parts by mass of methoxyethyl acrylate and 5 parts by mass of acrylic acid. Subsequently, 100 parts by mass of the acrylic polymer, 60 parts by mass of glyceryl tricaprylate, and 0.01 part by mass of the polyfunctional isocyanate compound were stirred and mixed to prepare an acrylic pressure-sensitive adhesive composition.

<Evaluation>
(Measurement of peel strength)
The base composition solution of each Example and each Comparative Example was applied to a copper foil (width 5 cm, length 10 cm) and dried at 130 ° C. for 5 minutes to make the upper surface of the copper foil stretchable to a thickness of 30 μm. A base material layer having was formed. As a result, a sample for measuring the peel strength was obtained.

Using a tensile tester (Shimadzu, "Autograph AGS50NX", desktop precision universal tester), fix the copper foil to the support base, cut the sample to a width of 1 cm, and peel off at an angle of 180 degrees. The base material layer was peeled from the copper foil by pulling it in the length direction under the condition of a peeling speed of 30 mm / min. Table 1 shows the measurement results of the peel strength at this time.

(Peelability of wiring)
A base material layer (thickness 8 μm) is formed using the base material composition solutions of each Example and each comparative example, and a pressure-sensitive adhesive layer (thickness 25 μm) is formed using the above acrylic pressure-sensitive adhesive composition. As a result, the laminates for biosensors shown in FIGS. 1 to 2B were manufactured. As wiring, copper wiring (thickness 4 μm, width (length in the lateral direction) 300 μm) was used. Further, the copper wiring was embedded in the base material groove of the base material layer, and the upper surface of the copper wiring was flush with the upper surface of the base material layer.

The laminated body for biosensors of each Example and each Comparative Example was attached to the joint portion (wrist) of the human body, and the joint was repeatedly bent.

At this time, the case where the copper wiring embedded in the base material groove on the upper surface of the base material layer is observed to completely protrude from the base material groove is evaluated as x, and the copper wiring protrudes from the base material groove. However, the case where a part that does not completely protrude is evaluated as △, and the case where only the upper part of the copper wiring slightly protrudes from the base material groove is evaluated as 〇, and the copper wiring is evaluated. The case where no change was observed was evaluated as ◎. The results are shown in Table 1.

Details such as the components listed in the table are shown below.

Polyurethane A: Trade name "Esstrane ET-370", manufactured by BASF, copolymer of diphenylmethane diisocyanate (8 mol%) and polytetramethylene ether glycol (92 mol%) Polyurethane B: Trade name "PANDEX T-8180N" KBM603, a copolymer of diphenylmethane diisocyanate (10 mol%) and polytetramethylene ether glycol (90 mol%), manufactured by DIC Cobestropolymer, trade name, manufactured by Shinetsu Chemical Co., Ltd., amine-based silane coupling agent, No. 1 Combined primary amine and secondary amine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane KBM903: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amino-based silane coupling agent, primary amine type, 3-Aminopropyltrimethoxysilane KBM403: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-based silane coupling agent, 3-glycidoxypropyltrimethoxysilane KBM503: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methacrylic-based silane coupling agent, 3-Methyloxypropyltrimethoxysilane KBM5103: trade name, manufactured by Shinetsu Chemical Co., Ltd., acrylic silane coupling agent, 3-acryloxypropyltrimethoxysilane KBE9007: trade name, manufactured by Shinetsu Chemical Co., Ltd., isocyanate-based silane coupling agent, 3-Ixapropyltriethoxysilane

1 Laminated body for biosensor 2 Pressure-sensitive adhesive layer 3 Base material layer 4 Wiring layer 30 Stick-on electrocardiograph 31 Electronic components

Claims (4)

A pressure-sensitive adhesive layer for sticking to a living body,
A base material layer arranged on the upper surface of the pressure-sensitive adhesive layer and having elasticity, and
A copper wiring layer embedded in the upper surface of the base material layer is provided.
The base material layer contains a polyurethane resin and an amine-based silane coupling agent, and the content of the amine-based silane coupling agent with respect to 100 parts by mass of the polyurethane resin is 0.1 to 10.0 parts by mass . A featured laminate for biosensors. The laminate for a biosensor according to claim 1 , wherein the amine-based silane coupling agent has a primary amine and a secondary amine. The biosensor according to claim 1 or 2 , wherein the amine-based silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and / or 3-aminopropyltrimethoxysilane. For laminate. The laminate for a biosensor according to any one of claims 1 to 3 and the laminate.
A biosensor comprising an electronic component mounted on the base material layer so as to be electrically connected to the copper wiring layer.

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