Porous insulating layer imparting object for bonding member for electrochemical element, laminate, electrode, electrochemical element, method for manufacturing laminate, method for manufacturing electrode, and method for manufacturing electrochemical element

Abstract

This porous insulating layer imparting object is provided with: a base material; and an adhesive porous insulating layer on the base material. The adhesive porous insulating layer is a porous structure having a co-continuous structure having a resin as a skeleton, and the resin is a crosslinked resin. In a peel strength measurement method using an element for measuring peel strength, the peel strength of an adhesive porous insulating layer is 2 N / m or more, and the element for measuring peel strength is obtained by: preparing a base material, as one of two base materials each having a size of 30 mm * 100 mm, forming a base material having a thickness of 30 mm * 100 mm; an adhesive porous insulating layer is provided by disposing an adhesive porous insulating layer on the entire surface of each of the two substrates, and the adhesive porous insulating layers face each other and are thermally bonded at a temperature of 140 DEG C and a cylinder thrust of 500 N for 1 minute.

Description

Technical Field

[0001] The present invention relates to a porous insulating layer imparting material for bonding components for an electrochemical element, a laminate, an electrode, an electrochemical element, a method for manufacturing a laminate, a method for manufacturing an electrode, and a method for manufacturing an electrochemical element. Background Art

[0002] In recent years, in daily life, smartphones, laptop computers, etc. have become popular, and electric vehicles without internal combustion engines have attracted attention worldwide with the development of a decarbonized society. These electronic devices are equipped with lithium-ion secondary batteries characterized by high output and high energy density.

[0003] In current general batteries, in most cases, they include electrodes that are not fixed to each other, and there is a problem that lamination misalignment may occur during electrode lamination. When electrode lamination misalignment occurs inside the battery, it will lead to a reduction in good battery performance and safety. Therefore, it is preferable to prevent electrode lamination misalignment.

[0004] Conventionally, as a secondary battery with less peeling of resin particles of an insulating layer laminated on an electrode active material layer, a secondary battery has been reported: having a porous insulating layer and a molten portion, the porous insulating layer being laminated by binding to the surface of at least one of a positive electrode active material layer and a negative electrode active material layer to cover at least one of the positive electrode active material layer and the negative electrode active material layer, the molten portion being formed at the edge of the insulating layer and cured in a state where pores disappear by melting of resin particles in the insulating layer (for example, refer to Patent Document 1).

[0005] In addition, as an electric storage device, an electric storage device having an electric storage unit and an electrolyte has been reported, wherein the electric storage unit includes: a first insulating layer that is bonded to a part of the surface of a positive electrode and a part of the surface of a negative electrode and separates the positive electrode and the negative electrode; and a region that is surrounded by the first insulating layer in a plan view and is used to hold an electrolyte between the positive electrode and the negative electrode; the air permeability of the first insulating layer is greater than 1250 seconds / 100 cc and less than 95000 seconds / 100 cc (for example, refer to Patent Document 2).

[0006] Citation List

[0007] Patent Document

[0008] [Patent Document 1] Japanese Unexamined Patent Application Publication No. 2016 - 33930

[0009] [Patent Document 2] WO2013 / 002138 Summary of the Invention

[0010] Technical Problem

[0011] An object of the present invention is to provide a porous insulating layer imparting material for bonding components for an electrochemical element, which can produce an insulating layer having excellent flexibility and ion permeability, can reduce the occurrence of layer misalignment of electrodes, and can produce an electrochemical element having excellent battery characteristics.

[0012] Solution to the problem

[0013] As a method for solving the above problems, a porous insulating layer imparting material for bonding components for an electrochemical element according to an embodiment of the present invention, the porous insulating layer imparting material includes: a substrate; and an adhesive porous insulating layer on the substrate; wherein, the adhesive porous insulating layer is a porous structure body having a co-continuous structure with a resin as a skeleton, and the resin is a crosslinked resin; wherein, in a peeling measurement method using a peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more, and the peeling strength measurement element is obtained as follows: Prepare a substrate, as one of two substrates each having a size of 30 mm × 100 mm, dispose the adhesive porous insulating layer over the entire surface of each substrate of the two substrates to provide the adhesive porous insulating layer, make the adhesive porous insulating layers face each other, and perform thermal bonding for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0014] Effect of the present invention

[0015] According to the present invention, it is possible to provide a porous insulating layer imparting material for bonding components for an electrochemical element, which can produce an insulating layer having excellent flexibility and ion permeability, can reduce the occurrence of layer misalignment of electrodes, and can produce an electrochemical element having excellent battery characteristics. Description of the drawings

[0016] A more complete understanding of the embodiments and many attendant advantages and features can be readily obtained and understood from the following detailed description with reference to the accompanying drawings.

[0017] Figure 1

[0018] Figure 1 is a schematic plan view of a coating area of a porous insulating layer according to an embodiment of the present invention.

[0019] Figure 2

[0020] Figure 2 is a schematic cross-sectional view of an electrode according to an embodiment of the present invention.

[0021] Figure 3

[0022] Figure 3 ​​​​​​It is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0023] Figure 4

[0024] Figure 4 It is a schematic cross-sectional view of an electrode according to an embodiment of the present invention.

[0025] Figure 5

[0026] Figure 5 It is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0027] Figure 6

[0028] Figure 6 It is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0029] Figure 7

[0030] Figure 7 It is a schematic plan view of a coating area of a porous insulating layer according to an embodiment of the present invention.

[0031] Figure 8

[0032] Figure 8 It is a schematic plan view of a coating area of a porous insulating layer according to an embodiment of the present invention.

[0033] Figure 9

[0034] Figure 9 It is a schematic cross-sectional view of an electrode according to an embodiment of the present invention.

[0035] Figure 10

[0036] Figure 10 It is a schematic cross-sectional view of an electrode according to an embodiment of the present invention.

[0037] Figure 11

[0038] Figure 11 It is a schematic cross-sectional view of an electrode according to an embodiment of the present invention.

[0039] Figure 12

[0040] Figure 12 It is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0041] Figure 13 ​​​​​​​​​​​​​​​​​​​​

[0042] Figure 13 is a schematic cross-sectional view of a layer stack according to an embodiment of the present invention.

[0043] Figure 14

[0044] Figure 14 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0045] Figure 15

[0046] Figure 15 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.

[0047] Figure 16A

[0048] Figure 16A is a schematic plan view of a porous insulating layer.

[0049] Figure 16B

[0050] Figure 16B is a schematic plan view of a porous insulating layer.

[0051] Figure 17

[0052] Figure 17 is a schematic diagram of a manufacturing apparatus for an adhesive porous insulating layer according to an embodiment of the present invention.

[0053] Figure 18

[0054] Figure 18 is as Figure 17 a schematic diagram of a liquid discharge apparatus as a modified example of the apparatus shown.

[0055] Figure 19

[0056] Figure 19 is a schematic diagram of a manufacturing apparatus for an adhesive porous insulating layer according to an embodiment of the present invention.

[0057] Figure 20

[0058] Figure 20 is a schematic diagram of a liquid discharge apparatus of a manufacturing apparatus for an adhesive porous insulating layer as an embodiment of the present invention.

[0059] Figure 21

[0060] Figure 21 is as​​​​​​​​​​​​​​​​​​Figure 20 Schematic diagram of a liquid discharge device as a modified example of the device shown.

[0061] Figure 22

[0062] Figure 22 It is a structural diagram of a printing unit using a drum-shaped intermediate transfer body of a manufacturing device for an adhesive porous insulating layer as an embodiment of the present invention.

[0063] Figure 23

[0064] Figure 23 It is a structural diagram of a printing unit using an annular belt-shaped intermediate transfer body of a manufacturing device for an adhesive porous insulating layer as an embodiment of the present invention.

[0065] The drawings are intended to depict embodiments of the present disclosure and should not be construed as limiting its scope. Unless explicitly stated, the drawings should not be regarded as drawn to scale. Also, throughout several views, the same or similar reference numerals denote the same or similar components. Detailed Description

[0066] When describing the embodiments shown in the drawings, specific terms are used for clarity. However, the disclosure of this specification is not intended to be limited to the specific terms selected, and it should be understood that each specific component includes all technical equivalents having similar functions, operating in a similar manner, and achieving similar results.

[0067] Hereinafter, embodiments of the present invention will be described with reference to the drawings. As used herein, the singular forms "a", "an", and "the" are also intended to include the plural forms unless the context clearly indicates otherwise.

[0068] (Porous Insulating Layer Imparter for Bonding Electrochemical Element Components)

[0069] ​​​​A porous insulating layer imparting material for bonding components for an electrochemical element according to an embodiment of the present invention has a substrate and an adhesive porous insulating layer on the substrate; the adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, and the resin is a cross-linked resin; wherein, in a peeling measurement method using a peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more; the peeling strength measurement element is obtained as follows: Prepare a substrate, and as one of two substrates each having a size of 30 mm × 100 mm, dispose the adhesive porous insulating layer over the entire surface of one side of each of the two substrates to provide the adhesive porous insulating layer, make the adhesive porous insulating layers face each other, and perform thermal bonding for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N. The porous insulating layer for bonding components for an electrochemical element is for the bonding use of components for an electrochemical element and has an adhesive insulating layer.

[0070] The porous insulating layer for bonding components for an electrochemical element according to an embodiment of the present invention was completed by the present inventors based on finding the following problems in the prior art.

[0071] That is, conventionally, a battery electrode (see Patent Document 1, etc.) in which an insulating adhesive is applied to suppress peeling of resin particles in an insulating layer has been known. However, a problem with such a battery electrode is that when a material that exhibits adhesiveness through thermal bonding is used, voids disappear due to melting of resin particles in the insulating layer, thereby reducing the porosity and resulting in a reduction in the insulation performance of the insulating layer.

[0072] The insulating adhesive is preferably a porous material that does not impede the circulation of the electrolyte inside the battery and has a high porosity. However, as shown in a power storage device of Patent Document 2, etc., if the air permeability (porosity) of the insulating layer becomes high, there is a problem of a reduction in the strength of the insulating layer.

[0073] In particular, in battery applications such as battery elements such as batteries and power generation elements such as fuel cells, when a conventional porous structure is formed on an electrode as a substrate and used as an insulating layer, when the porosity of the porous structure decreases, the permeability of substances becomes insufficient, it is difficult to maintain ion permeability, and there is a problem of a reduction in battery performance.

[0074] In addition, since a layer shift of the electrodes inside the battery will cause a reduction in good battery performance and safety, it is preferable to reduce the occurrence of layer shift of the electrodes. Based on this view, it is preferable that the trade-off relationship between the ion permeability (porosity) of the insulating layer and the strength of the insulating layer is compatible, and the insulating layer has sufficient flexibility in addition to strength to cope with the layer shift of the electrodes.

[0075] The inventors of the present invention have conducted in-depth research to solve the above problems, and as a result, it has been found that a porous insulating layer for bonding components for an electrochemical element according to an embodiment of the present invention can provide a porous insulating layer-imparted material for bonding components for an electrochemical element, which can produce an insulating layer with excellent flexibility and ion permeability, can reduce the occurrence of layer misalignment of electrodes, and can produce an electrochemical element with excellent battery characteristics, thus completing the present invention.

[0076] <Substrate>

[0077] The substrate can be any material, whether transparent or opaque, and can be appropriately selected according to the purpose.

[0078] As the transparent substrate, there is no particular limitation, and examples thereof may include a glass substrate, a resin film substrate such as various plastic films, and a composite substrate thereof.

[0079] As the opaque substrate, for example, a metal substrate such as a silicon substrate, stainless steel, aluminum, or copper, a recording medium, and a laminate thereof can be cited, but it is not limited thereto.

[0080] The recording medium can be ordinary paper, glossy paper, special paper, or fabric, or a low-permeability substrate (low-absorbency substrate). The low-permeability substrate refers to a substrate with low water permeability, absorbency, and adsorbency on the surface, and also includes a substrate having a plurality of hollow portions inside but not opening to the outside. As the low-permeability substrate, there is no particular limitation, and examples thereof may include coated paper used in commercial printing, a recording medium such as a surface-coated cardboard having an intermediate layer and a back layer containing waste paper pulp.

[0081] The substrate can be a porous insulating layer such as a porous resin sheet used as an insulating layer for an electrochemical element, a paper separator containing cellulose fibers, an electrode substrate for an electrochemical element, or an electrode composite layer provided on the electrode substrate.

[0082] The shape of the substrate can be curved or uneven, and a substrate that can be appropriately selected and used in an imparting unit or a polymerization unit of a manufacturing apparatus applicable to a laminate can be used.

[0083] <Adhesive porous insulating layer>

[0084] The adhesive porous insulating layer is disposed on the substrate.

[0085] The adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, having a peel strength of 2 N / m or more and having thermo-bonding properties.

[0086] In this specification and the claims, the term "thermal adhesiveness" means adhesiveness to another substance caused by heating. As an example of the discovery of adhesiveness, an increase in the peel strength between a structure having thermal adhesiveness by heating and other substances can be cited.

[0087] The volume resistivity of the adhesive porous insulating layer is preferably 1×10 12 (Ω·cm) or more.

[0088] - Porous structure -

[0089] The porous structure (hereinafter sometimes referred to as porous resin) has a co - continuous structure with resin as the skeleton.

[0090] The resin is preferably a cross - linked resin, which is a polymer of a polymerizable compound that can be polymerized by energy irradiation.

[0091] Here, the so - called "co - continuous structure" means a structure in which two or more substances or phases each have a continuous structure and do not form an interface. In this embodiment, it means a structure in which both the resin phase and the pore phase form a three - dimensional branched network continuous phase. Such a structure can be formed, for example, by polymerizing the following liquid composition by the polymerization - induced phase separation method.

[0092] [Glass transition temperature]

[0093] When the resin is a cross - linked resin, heating imparts adhesiveness for bonding to another substance, and does not cause the cross - linked resin to melt, making it less likely to cause large shape changes. Thus, the adhesive porous insulating layer can maintain good insulation properties both before and after thermal bonding.

[0094] In order for the adhesive porous insulating layer to function as an adhesive layer, the glass transition temperature (Tg) of the cross - linked resin that forms the skeleton is important.

[0095] The glass transition temperature (Tg) of the adhesive porous insulating layer is preferably 0°C or more and 100°C or less, more preferably 25°C or more and 60°C or less.

[0096] When Tg is lower than 0°C, the cross - linked resin is sticky on the surface at normal temperature, making the treatment after forming the adhesive porous insulating layer difficult, so it is not preferred.

[0097] When Tg is higher than 100°C, it is difficult to obtain good adhesiveness by thermal bonding, and thermal bonding requires high temperature, so sometimes it may have an adverse effect on the surrounding substrates due to overheating, so it is not preferred. On the other hand, when Tg is 0°C or more and 100°C or less, it is preferred from the viewpoints of operability before and after thermal bonding, adhesiveness after thermal bonding, and no adverse effects caused by overheating.

[0098] By making the porous structure have a co - continuous structure with a three - dimensional branched network structure as the skeleton, a porous structure with high porosity and high strength can be achieved.

[0099] That is, as Figure 16A and Figure 16B shown, the adhesive porous insulating layer 10b has a plurality of pores 10x, and one pore 10x has connectivity with another pore 10x around the one pore 10x, and extends three - dimensionally.

[0100] The porous structure has a co - continuous structure. Through the connection between pores, the electrolyte can fully penetrate without hindering ion movement.

[0101] As a method for confirming the co - continuous structure and pore connection, for example, a method of observing the cross - sectional image of the porous structure by a scanning electron microscope (SEM) and confirming the continuous connection between pores can be cited. As a physical property obtained through pore connection, air permeability can be cited.

[0102] [Observation of images using a scanning electron microscope (SEM), measurement of porosity]

[0103] The porosity of the porous structure is preferably 30% or more, more preferably 50% or more, and also preferably 90% or less, more preferably 85% or less.

[0104] By making the porosity 30% or more, liquids or gases can fully penetrate, and functions such as substance separation and reaction fields can be effectively exerted. When the porous structure is used as an insulating layer of an energy storage element, the permeability of the electrolyte and the ion permeability are improved, and the internal reaction of the energy storage element proceeds efficiently. When the porosity is 90% or less, the strength of the porous structure is improved.

[0105] There is no particular limitation on the method for evaluating the porosity of the porous structure, and it can be appropriately selected according to the purpose. For example, a method of osmium staining the porous structure, cutting out the internal cross - sectional structure with a focused ion beam (FIB), and measuring the porosity with a scanning electron microscope (SEM) can be cited, but it is not limited thereto.

[0106] In particular, the porosity can be measured through the following steps.

[0107] That is, the porous structure is cut into a size of 5 mm×10 mm and osmium - stained with osmium(VIII) oxide (manufactured by Nisshin EM Co., Ltd.). The cut adhesive porous insulating layer is placed in a bottle containing a small amount of aqueous solution, kept from contacting the aqueous solution, and left standing in a sealed bottle for 30 minutes for staining. Then, the layer is dried in ventilation for 1 hour to provide a sample.

[0108] After sufficient drying, the sample was vacuum-impregnated with a two-component epoxy resin (manufactured by ITW Performance Polymers Fluids Japan). Then, the cross-section was cut at 5.0 kV using a cross-section polisher (manufactured by JEOL Ltd.), and observed using cryoFIB / SEM (manufactured by FEI Company, Japan).

[0109] The porosity of the porous structure is calculated by binarizing the observed image and deriving the proportion of voids in the observed area.

[0110] [Air permeability]

[0111] The air permeability of the porous structure is preferably 1000 seconds / 100 mL or less, more preferably 500 seconds / 100 mL or less, and even more preferably 300 seconds / 100 mL or less.

[0112] The air permeability is the air permeability measured according to JIS P8117, and can be measured using, for example, a Gurley-type air permeability tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.).

[0113] For example, the connection of pores can be determined by showing an air permeability of 1,000 seconds / 100 mL or less.

[0114] The cross-sectional shape of the pores of the porous resin can have various shapes, such as substantially circular, substantially elliptical, or substantially polygonal, and various sizes. Here, the size of the pore refers to the length of the longest part in the cross-sectional shape of the pore. The size of the pore can be obtained from a cross-sectional image taken with a scanning electron microscope (SEM).

[0115] The size of the pores of the porous resin is not particularly limited and can be appropriately selected according to the purpose. However, considering the liquid or gas permeability, it is preferably 0.01 μm or more and 10 μm or less.

[0116] By making the voids 0.1 μm or more and 10 μm or less, the liquid or gas can permeate sufficiently, and functions such as substance separation and provision of a reaction field can be effectively exerted. As described later, in the case where the porous structure is used as an insulating layer of a power storage element, by making the voids 10 μm or less, short circuit between the positive electrode and the negative electrode due to lithium dendrites generated inside the power storage element can be prevented, and safety can be improved.

[0117] The method for adjusting the pore size and porosity of the porous resin to the above ranges is not particularly limited. For example, methods such as adjusting the content of the polymerizable compound in the liquid composition to the above range, adjusting the content of the pore former in the liquid composition to the above range, and adjusting the irradiation conditions of active energy rays can be cited, but are not limited to these methods.

[0118] The average thickness of the adhesive porous insulating layer is not particularly limited and can be appropriately selected according to the purpose. It is preferably 1.0 μm or more and 150.0 μm or less, more preferably 10.0 μm or more and 100.0 μm or less. By making the average thickness 10.0 μm or more, good bonding strength can be obtained during thermal bonding with other electrodes. By making the average thickness 100.0 μm or less, flexibility can be imparted to the adhesive porous insulating layer.

[0119] The average thickness is appropriately adjusted according to the use of the porous resin.

[0120] Most preferably, the average thickness is adjusted according to the thickness of the opposing electrode. As Figure 13 shown, it is preferable that in the cross-sectional structure after forming the unit, the thickness of the space formed by the adhesive layer has a thickness comparable to the film thickness of the opposing electrode. Thereby, the strain generated at the end of the stacked electrodes after battery stacking can be reduced.

[0121] The average thickness can be obtained by measuring the thickness at any three or more points and calculating their average value.

[0122] The term "thickness" refers to the thickness formed only by the porous resin layer. For example, when the porous resin layer penetrates into the substrate, the thickness of the layer including the porous resin layer and the substrate is not calculated.

[0123] The adhesive porous insulating layer can be thermally bonded, for example, when combined with the electrode coated with the adhesive porous insulating layer and other electrodes, and can reduce the electrode layer stacking deviation generated during or after the battery stacking process. Therefore, as long as the formation site of the adhesive porous insulating layer can exhibit the above-mentioned adhesive effect, it is not particularly limited, and the adhesive porous insulating layer can be formed at any position such as on the electrode substrate, on the electrode composite material layer, on the porous insulating layer, etc. However, when disposed on the surface facing the counter electrode, the above functions can be obtained, but in order not to hinder the ion permeability between the electrodes, it is preferable to form the adhesive porous insulating layer in a region not facing the counter electrode.

[0124] [Peeling strength]

[0125] The peeling strength of the adhesive porous insulating layer is the peeling strength measured by the peeling measurement method at room temperature (25 °C) when using the peeling strength measurement element.

[0126] The peeling strength of the adhesive porous insulating layer is 2 N / m or more, preferably 5 N / m or more, more preferably 25 N / m or more.

[0127] The element for measuring peel strength is fabricated as follows: Prepare two substrates measuring 30 mm × 100 mm. On one side of each substrate, a bonding porous insulating layer is disposed over the entire surface. The bonding porous insulating layers are positioned opposite to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0128] For measuring the peel strength, for example, a bonding / laminating peel analysis device Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.), which is a peel strength measurement device, can be used. Specifically, the measurement can be carried out according to the following steps.

[0129] The surface of the base a of the element for measuring peel strength that faces the side where the bonding porous insulating layer is formed and the specimen fixing surface in the peel strength measurement device are fixed by a thin double-sided tape. Then, the surface of the base b of the element for measuring peel strength that is opposite to the side where the bonding porous insulating layer is formed and the tensile indenter of the peel strength measurement device are fixed with a tape. The peel strength is measured under the following measurement conditions.

[0130] - Measurement conditions for peel strength -

[0131] - Peel strength measurement device: Bonding / Laminating Peel Analysis Device Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.)

[0132] - Thin double-sided tape: No. 5000NS (width 20 mm, manufactured by Nitto Denko Corporation)

[0133] - Tape: No. 29 (width 18 mm, manufactured by Nitto Denko Corporation)

[0134] - Measurement speed: 30 mm / min

[0135] - Peel angle: 90°

[0136] - Peel distance: 75 mm

[0137] The peel distance does not significantly contribute to the peel strength. Therefore, it can be any value. The thin double-sided tape and the tape used for fixing the element for measuring peel strength can have a peel strength sufficiently higher than the peel strength of the bonding porous insulating layer, and a tape that will not peel during the measurement can be appropriately selected.

[0138] (Laminated body)

[0139] The laminated body of the first embodiment of the present invention includes a porous insulating layer imparting material for bonding components for an electrochemical element according to one embodiment of the present invention described above, and another substrate bonded through at least a part of the bonding porous insulating layer.

[0140] In addition, the laminate according to the second embodiment of the present invention includes a first substrate and a second substrate; wherein, the first substrate has a first adhesive porous insulating layer; wherein, the first substrate and the second substrate are bonded via the first adhesive porous insulating layer; wherein, the first adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton; wherein, the resin is a crosslinked resin; wherein, in the peeling measurement method using a peeling strength measurement element, the peeling strength of the first adhesive porous insulating layer is 2 N / m or more, and the peeling strength measurement element is obtained as follows: The first adhesive porous insulating layer is disposed on one entire surface of a 30 mm × 100 mm first substrate and one entire surface of a 30 mm × 100 mm second substrate such that the first adhesive porous insulating layers face each other, and heat bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0141] Preferably, the second substrate has a second adhesive porous insulating layer, and the first substrate and the second substrate are laminated in such a manner that the first adhesive porous insulating layer and the second adhesive porous insulating layer face each other.

[0142] In one aspect, the laminate may include an electrode as the first substrate and a separator as the second substrate. In another aspect, the laminate may include an electrode as the first substrate and an electrode as the second substrate. Both aspects can be preferably adopted.

[0143] The peeling strength of these adhesive porous insulating layers is 2 N / m or more, and the adhesiveness is excellent. Therefore, in the case of having an interface between the first adhesive porous insulating layer and each substrate, and a second adhesive porous insulating layer, sufficient adhesiveness at the interface between the second adhesive porous insulating layer and the second substrate, and the interface between the first adhesive porous insulating layer and the second adhesive porous insulating layer can also be ensured, while the content of the adhesive in the first adhesive porous insulating layer or the second adhesive porous insulating layer can be suppressed. When the first adhesive porous insulating layer or the second adhesive porous insulating layer contains an adhesive, the melting of the adhesive may cause the pores of the first adhesive porous insulating layer or the second adhesive porous insulating layer to be blocked, thereby unable to maintain the porous structure and reducing the battery characteristics.

[0144] The content of the adhesive in the first adhesive porous insulating layer is preferably 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 10% by mass or less as a content substantially free of the adhesive, further preferably 0% by mass or more and 5% by mass or less, and even more preferably 0% by mass.

[0145] In the case where there is a second adhesive porous insulating layer, the content of the above-mentioned adhesive is specified relative to the total amount of the first adhesive porous insulating layer and the second adhesive porous insulating layer.

[0146] <Other substrates, the first substrate, and the second substrate>

[0147] Regarding the above-mentioned other substrates, the first substrate, and the second substrate, the matters described in the above substrates can be appropriately selected.

[0148] The substrate can be a porous resin sheet, a porous insulating layer, a paper separator containing cellulose fibers, etc. used as an insulating layer for an electrochemical element, or can be an electrode substrate for an electrochemical element, an electrode composite layer on an electrode substrate, etc.

[0149] 《Porous insulating layer》

[0150] In order to ensure battery performance and prevent short circuits, the porous insulating layer can be provided on the active material, or provided on the electrode substrate and adjacent to the active material.

[0151] The porous insulating layer is not particularly limited, and the layer of the porous body can be appropriately selected according to the purpose. It is a structure having a plurality of pores and has a volume resistivity of 1×10 12 (Ω·cm) or more. For example, a sheet-like insulating layer mainly made of materials such as polyolefin and cellulose, an insulating layer integrated with a substrate formed on a substrate such as an electrode, etc. can be cited.

[0152] Particularly preferably, the porous insulating layer is a porous structure body having a co-continuous structure with a crosslinked resin as a skeleton and is a porous insulating layer with a peel strength of less than 2 N / m.

[0153] Regarding the porous structure body in the porous insulating layer, particularly regarding the properties other than the peel strength and the glass transition temperature, the matters described in the porous structure body in the adhesive porous insulating layer can be appropriately selected.

[0154] As long as the peel strength of the porous structure body is lower than 2 N / m, there is no particular limitation and it can be appropriately selected according to the purpose.

[0155] The glass transition temperature of the porous structure body is not particularly limited and can be appropriately selected according to the purpose.

[0156] As a manufacturing method of the porous structure body in the porous insulating layer, the liquid composition, polymerizable compound, liquid, polymerization-induced phase separation, etc. described in the porous structure body in the adhesive porous insulating layer can be appropriately selected.

[0157] The average thickness of the porous resin is not particularly limited and can be appropriately selected according to the purpose. However, considering the curing uniformity during polymerization, it is preferably 0.01 μm or more and 500 μm or less, more preferably 0.01 μm or more and 100 μm or less, further preferably 1 μm or more and 50 μm or less, and particularly preferably 10 μm or more and 20 μm or less. If the film thickness is 0.01 μm or more, the surface area of the obtained porous resin becomes larger, and the functions of the porous resin can be fully exerted. On the other hand, by making the film thickness 500 μm or less, the unevenness in the film thickness direction of light and heat used during polymerization can be reduced, and a porous resin that is uniform in the film thickness direction can be obtained. By manufacturing a porous resin that is uniform in the film thickness direction, the structural non-uniformity of the porous resin can be reduced, and the reduction in the permeability of liquid or gas can be prevented.

[0158] When using the porous resin as an insulating layer for an electrochemical element, the average thickness of the porous insulating layer is not particularly limited and can be appropriately selected according to the purpose. It is preferably 1.0 μm or more and 50.0 μm or less, more preferably 5.0 μm or more and 20.0 μm or less. By making the average thickness 5.0 μm or more, short circuits caused by the unevenness of the active material are less likely to occur, and by making the average thickness 20.0 μm or less, the battery characteristics are good.

[0159] The porous insulating layer is mainly provided in the region where the first electrode and the second electrode face each other. That is, this region is the region that represents the reaction field of ions in the secondary battery, and by making the film thickness of the formed porous insulating layer thinner, better battery characteristics can be obtained.

[0160] Here, the term "thickness" refers to the thickness formed only by the porous resin layer. For example, when the porous resin layer penetrates into the substrate, the thickness of the layer including the porous resin layer and the substrate is not calculated.

[0161] Figures 1 to 3 Shows an example of the porous insulating layer imparting material (electrode) for bonding components for an electrochemical element in this embodiment, and the laminate (electrochemical element). Figure 1 and Figure 2 respectively show the top view and cross-sectional view of this embodiment, Figure 1 indicating the coating area of the adhesive porous insulating layer 10b. In this embodiment, on one side (on the first electrode composite layer 9) of the substrate of the first electrode composite layer 9 provided on both sides of the first electrode substrate 8, a porous insulating layer 10a is provided, and an adhesive porous insulating layer 10b is provided in the blank portion around the porous insulating layer 10a on the substrate.

[0162] Figure 3 represents having Figure 1 and Figure 2Cross-sectional view of a laminate (electrochemical element) of the electrodes shown. In Figure 3 In the laminate, Figure 1 and Figure 2 The electrodes (first electrodes) shown and electrodes (first electrodes) having the same structure sandwich a second electrode provided with second electrode composite layers 12 on both sides of a second electrode substrate 11, and two separated first electrode composite layers 9 are bonded by an adhesive porous insulating layer 10b.

[0163] The adhesive porous insulating layer 10b is disposed on the outermost surface of the electrode, that is, the portion exposed to the electrode surface. In the present embodiment, it is disposed on at least a part of the outer peripheral portion of the side surface of the electrode. Since the adhesive porous insulating layer 10b has excellent ion permeability, it does not hinder the circulation of the electrolyte in the battery. Since the insulating layer has flexibility, the generation of laminate shift of the electrodes can be reduced, and good battery characteristics and safety can be obtained.

[0164] Figure 1 , Figures 4 to 5 An example of a porous insulating layer imparting material (electrode) for bonding components for an electrochemical element and a laminate (electrochemical element) showing another embodiment. Figure 1 and Figure 4 respectively show a top view and a cross-sectional view of the present embodiment, Figure 1 showing the coating region of the adhesive porous insulating layer 10b. In the present embodiment, a porous insulating layer 10a is provided on the entire surface of one surface (on the first electrode composite layer 9) of a base material having first electrode composite layers 9 provided on both sides of a first electrode substrate 8, and an adhesive porous insulating layer 10b is provided around the porous insulating layer 10a.

[0165] Figure 5 is a cross-sectional view of a laminate (electrochemical element) having Figure 1 and Figure 4 the electrodes shown. In Figure 5 the laminate, Figure 1 and Figure 4 the electrodes (first electrodes) shown and electrodes (first electrodes) having the same structure sandwich the second electrode, and two separated first electrode composite layers 9 are bonded by an adhesive porous insulating layer 10b.

[0166] Figure 6 The laminate shown represents Figure 5 a modified example of the laminate in Figure 5Compared with the laminate, the end of the second electrode substrate 11 extends from the end of the second electrode composite layer 12, and the second electrode substrate 11 is bonded to the first electrode composite layer 9 via the adhesive porous insulating layer 10b. Similarly, the other first electrode composite layer 9 is also bonded to the other side of the second electrode substrate 11 via the adhesive porous insulating layer 10b.

[0167] Figures 7 to 11 An example of a porous insulating layer imparting material (electrode) for bonding electrochemical element components and a laminate (electrochemical element) showing another embodiment.

[0168] As Figure 7 and Figure 8 As shown in the top view, from other modification examples of the coating area of the adhesive porous insulating layer 10b, it is also possible not to provide the porous insulating layer 10a, but to provide the adhesive porous insulating layer 10b ( Figure 7 ) on the first electrode composite layer 9 (substrate), and then, provide the sheet-like separator 13 to replace the porous insulating layer 10a ( Figure 8 ). Figure 9 is a cross-sectional view corresponding to Figure 7 , Figure 10 is a cross-sectional view corresponding to Figure 8 , Figure 11 is a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Figure 8 and Figure 10 .

[0169] In addition, Figures 12 to 13 and Figures 14 to 15 show an example of a porous insulating layer imparting material (electrode) for bonding electrochemical element components and a laminate (electrochemical element) showing other embodiments.

[0170] As Figures 12 to 13 , Figures 14 to 15 shown, the first electrode composite layer 9 is provided on both sides of the first electrode substrate 8, but it is also possible to expose the peripheral portion of the first electrode substrate 8 and provide the adhesive porous insulating layer 10b on the exposed first electrode substrate 8.

[0171] Figures 12 to 13 shows the mode using the sheet-like separator 13 as the insulating layer, Figures 14 to 15 shows the mode using the porous insulating layer 10a as the insulating layer. Figure 13 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Figure 12 , Figure 15 shows a cross-sectional view of a laminate (electrochemical element) having the electrodes shown in Figure 14 .

[0172] Figure 3, Figure 5 , Figure 6 , Figure 11 , Figure 13 and Figure 15 All of the laminates in [[ID=]] and [[ID=]] are electrochemical elements in which a first electrode and a second electrode insulated from the first electrode are laminated.

[0173] (Method for manufacturing a laminate and apparatus for manufacturing a laminate)

[0174] The method for manufacturing a laminate according to an embodiment of the present invention includes an adhesive porous insulating layer forming step, a lamination step, and an adhesion step, and further includes other steps as needed.

[0175] The apparatus for manufacturing a laminate according to an embodiment of the present invention includes an adhesive porous insulating layer forming unit, a lamination unit, and an adhesion unit, and further includes other units as needed.

[0176] (Adhesive porous insulating layer forming step and adhesive porous insulating layer forming unit)

[0177] [Method for manufacturing a porous insulating layer imparting material for bonding components for an electrochemical element]

[0178] The adhesive porous insulating layer forming step is a step of forming a first adhesive porous insulating layer on a first substrate, and can be suitably carried out by an adhesive porous insulating layer forming unit.

[0179] The adhesive porous insulating layer forming unit is a unit for forming a first adhesive porous insulating layer on a first substrate.

[0180] The first adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, and the resin is a crosslinked resin. In the peeling measurement method using a peeling measurement element, the peeling strength of the first adhesive porous insulating layer is 2 N / m or more, and the peeling measurement element is obtained as follows: Prepare a substrate, which is one of two substrates each having a size of 30 mm × 100 mm, and dispose the adhesive porous insulating layer on the entire surface of one side of each of the two substrates to provide the adhesive porous insulating layer, and make the adhesive porous insulating layers face each other, and perform thermal bonding for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0181] Through the adhesive porous insulating layer forming step, it is possible to suitably manufacture the porous insulating layer imparting material for bonding components for an electrochemical element according to one embodiment of the present invention described above.

[0182] The process for forming the adhesive porous insulating layer includes: a dispensing process of dispensing a liquid composition onto a first substrate, and a polymerization process of polymerizing the liquid composition by applying heat or light thereto, and further includes other processes as needed.

[0183] The adhesive porous insulating layer forming unit includes: a storage container for storing the liquid composition, a dispensing unit for dispensing the liquid composition stored in the storage container onto a substrate, a polymerization unit for polymerizing the liquid composition by applying heat or light thereto, and further has other units as needed.

[0184] - Liquid composition -

[0185] The liquid composition contains a polymerizable compound and a liquid, and further contains other components such as a polymerization initiator as needed.

[0186] The liquid composition forms a porous resin, the light transmittance at a wavelength of 550 nm measured while stirring the liquid composition is 30% or more, and the rising rate of the haze value in the haze measurement element prepared by polymerizing the liquid composition is 1.0% or more.

[0187] The liquid composition forms a porous structure. That is, through the polymerization and curing of the polymerizable compound in the liquid composition, a resin structure (also referred to as "porous resin" or "porous structure") having a porous structure with a resin as the skeleton is formed.

[0188] When the peel strength of the insulating layer formed from the porous structure is 2 N / m or more, the insulating layer corresponds to the adhesive porous insulating layer in the porous insulating layer imparting material for bonding components for an electrochemical element of the present invention, and corresponds to the first adhesive porous insulating layer in the laminate of the present invention.

[0189] When the peel strength of the insulating layer formed from the porous structure is less than 2 N / m, the above-mentioned porous insulating layer corresponds to other porous insulating layers.

[0190] Here, the term "the liquid composition forms a porous resin" means not only including the case where a porous resin is formed in the liquid composition, but also including the case where a precursor of the porous resin (for example, the skeleton of the porous resin) is formed in the liquid composition, and then the porous resin is formed through subsequent processing (for example, heat treatment).

[0191] -- Polymerizable compound --

[0192] The polymerizable compound forms a resin through polymerization, and forms a porous resin according to the composition and characteristics of the liquid composition.

[0193] As a polymerizable compound, there is no particular limitation as long as it is a compound that forms a polymer (resin) by polymerization. Known polymerizable compounds can be appropriately selected according to the purpose, but those having at least one radically polymerizable functional group are preferred.

[0194] Preferred examples of the polymerizable compound may include, but are not limited to, radically polymerizable compounds such as monofunctional, difunctional, or trifunctional or higher radically polymerizable monomers, radically polymerizable oligomers; functional monomers and functional oligomers further having functional groups other than the polymerizable functional group. Difunctional or higher radically polymerizable compounds are particularly preferred.

[0195] As the polymerizable group of the polymerizable compound, at least one of (meth)acryloyl and vinyl is preferred, and (meth)acryloyl is more preferred.

[0196] The polymerizable compound is preferably polymerized by irradiation with energy, and more preferably polymerized by heat or light.

[0197] The resin formed from the polymerizable compound is preferably a resin that forms a network-like structure by irradiation with active energy rays (such as light irradiation, heating). Preferred examples include, but are not limited to, acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, oxetane resins, vinyl ether resins, and resins formed by ene-thiol reactions.

[0198] In particular, from the viewpoint of easily forming a structure by highly reactive radical polymerization, resins formed from polymerizable compounds having (meth)acryloyl such as acrylate resins, methacrylate resins, and urethane acrylate resins are more preferred, and from the viewpoint of productivity, resins formed from polymerizable compounds having vinyl such as vinyl ester resins are more preferred.

[0199] These can be used alone or in combination. When two or more resins are used in combination, there is no particular limitation on the combination of the polymerizable compounds, and they can be appropriately selected according to the purpose. For example, in order to impart flexibility, it is preferred to mix a urethane acrylate resin as the main component with other resins. A polymerizable compound having at least one of acryloyl and methacryloyl is referred to as a polymerizable compound having (meth)acryloyl.

[0200] The active energy ray is not particularly limited as long as it is a ray that can impart the energy required for the polymerization reaction of the polymerizable compound in the liquid composition. Examples thereof include, but are not limited to, ultraviolet rays, electron beams, α rays, β rays, γ rays, and X rays. Ultraviolet rays are particularly preferred. Especially when using a high-energy light source, the polymerization reaction can be carried out without using a polymerization initiator.

[0201] As the monofunctional free-radical polymerizable compound, there is no particular limitation, and examples thereof include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, etc. These can be used alone or in combination of two or more.

[0202] As the bifunctional free-radical polymerizable compound, there is no particular limitation, and examples thereof include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, E0-modified bisphenol A diacrylate, E0-modified bisphenol F diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, etc. These can be used alone or in combination of two or more.

[0203] As the trifunctional or higher-functional free-radical polymerizable compound, there is no particular limitation, and examples thereof include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, E0-modified trimethylolpropane triacrylate, P0-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, E0-modified glycerol triacrylate, P0-modified glycerol triacrylate, tris(acryloyloxy)isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dihydroxymethylpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, E0-modified tris(acryloyloxy)phosphate, 2,2,5,5-tetramethylolcyclopentanone tetraacrylate, etc. These can be used alone or in combination of two or more.

[0204] The content of the polymerizable compound is preferably 5.0% by mass or more and 70.0% by mass or less, more preferably 10.0% by mass or more and 50.0% by mass or less, and still more preferably 20.0% by mass or more and 40.0% by mass or less, based on the total amount of the liquid composition.

[0205] The content is preferably 70.0% by mass or less. In this way, the pore size of the resulting porous body will not be too small (less than a few nanometers), thereby providing a porous body with an appropriate porosity and avoiding the tendency of poor liquid or gas permeability. On the other hand, from the aspect of forming a three-dimensional network structure that can sufficiently obtain a porous structural body and the tendency of the strength of the resulting porous structural body to increase, it is preferably 5.0% by mass or more.

[0206] --Liquid--

[0207] The liquid contains a pore-forming agent and, if necessary, other liquids other than the pore-forming agent.

[0208] The pore-forming agent is a liquid that is miscible with the polymerizable compound and is immiscible (phase separation occurs) with the resulting polymer (resin) during the polymerization of the polymerizable compound in the liquid composition. The presence of the pore-forming agent in the liquid composition causes a porous resin to be formed during the polymerization of the polymerizable compound. The pore-forming agent can also preferably dissolve a compound (a polymerization initiator described later) that generates free radicals or acids by light or heat.

[0209] The liquid or the pore-forming agent can be used alone or in combination with others.

[0210] In this embodiment, the liquid is not polymerizable.

[0211] The boiling point of one kind or a combination of two or more kinds of these pore-forming agents is preferably 50°C or more and 250°C or less, more preferably 70°C or more and 200°C or less, and still more preferably 120°C or more and 190°C or less under normal pressure. By setting the boiling point to 50°C or more, it is possible to prevent the pore-forming agent from vaporizing near room temperature, making the handling of the liquid composition easier and facilitating the control of the content of the pore-forming agent in the liquid composition. On the other hand, when the boiling point is 250°C or less, the time required for the step of removing the pore-forming agent after polymerization becomes shorter, and thus the productivity of the porous resin is improved. In addition, since the amount of the pore-forming agent remaining inside the porous resin can be reduced, the quality can be improved when the porous resin is used as a functional layer such as a separation layer for separating substances or a reaction layer serving as a reaction field.

[0212] Examples of the pore former include, but are not limited to, glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc., esters such as γ-butyrolactone, propylene carbonate, etc., amides such as N,N-dimethylacetoacetamide, etc. The examples also include, but are not limited to, liquids with relatively large molecular weights such as methyl myristate, methyl caprate, methyl myristate, tetradecane, etc. The examples also include, but are not limited to, liquids such as acetone, 2-ethylhexanol, 1-bromonaphthalene, etc.

[0213] In addition, not all of the above-listed liquids necessarily belong to the pore former.

[0214] As described above, the pore former is a liquid that is miscible with the polymerizable compound and immiscible (phase-separates) with the polymer (resin) obtained during the polymerization of the polymerizable compound in the liquid composition. That is, whether a liquid becomes a pore former depends on its relationship with the polymerizable compound and the resulting polymer (the resin formed by the polymerization of the polymerizable compound).

[0215] The liquid composition preferably contains at least one pore former having the above specific relationship with the polymerizable compound, thereby providing a wider range of choices for the materials when preparing the liquid composition and making it easier to design the liquid composition. By having a wider range of choices for the materials when preparing the liquid composition, when characteristics are required for the liquid composition from viewpoints other than forming a porous structure, there can be a wider range of choices.

[0216] For example, when the liquid composition is discharged by an inkjet method, from viewpoints other than forming a porous structure, the liquid composition is required to have discharge stability, and a wider range of material choices is beneficial for the design of the liquid composition.

[0217] The content of the liquid or pore former, based on the total amount of the liquid composition, is preferably 30.0% by mass or more and 95.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, and still more preferably 60.0% by mass or more and 80.0% by mass or less.

[0218] The content of the liquid or pore former is preferably 30.0% by mass or more because the pore size of the resulting porous body will not be too small to be less than a few nanometers, so that the porous body has an appropriate porosity and can suppress the tendency of poor liquid or gas permeability. On the other hand, considering the aspect of forming a three-dimensional network structure that can sufficiently obtain a porous structure and the tendency of the strength of the resulting porous structure to increase, the content of the liquid or pore former is preferably 95.0% by mass or less.

[0219] As described above, since it is sufficient to contain at least one pore former having the above specific relationship with the polymerizable compound, other liquids (non-pore former liquids) that do not have the above specific relationship with the polymerizable compound can also be further contained.

[0220] The content of the above other liquid is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably 0% by mass (excluding) based on the total amount of the liquid composition.

[0221] The mass ratio of the content of the polymerizable compound to the content of the pore-forming agent in the liquid composition (polymerizable compound:pore-forming agent) is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, and still more preferably 1.0:1.5 to 1.0:4.0.

[0222] --Other components--

[0223] ---Polymerization initiator---

[0224] The liquid composition may contain other components such as a polymerization initiator.

[0225] The polymerization initiator is a material that can generate an active substance such as a radical or a cation through energy such as light or heat and initiate the polymerization of the polymerizable compound. As the polymerization initiator, there is no particular limitation, and known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be cited. These materials can be used alone or in combination. A photo radical polymerization initiator is particularly preferred.

[0226] As the above photo radical polymerization initiator, there is no particular limitation, and a known photo radical polymerization initiator can be appropriately selected according to the purpose. Examples thereof include, but are not limited to, photo radical polymerization initiators such as Michler's ketone or benzophenone known under the trade names IRGACURE or DAROCUR.

[0227] As specific compounds, benzophenone, acetophenone derivatives can be cited. For example, α-hydroxy or α-aminobenzophenone, 4-aroyl-1,3-dioxocyclopentyloxy, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzil, benzoin, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoylformate, isopropyl ether of zonene, benzoin methyl ether, benzoin ethyl ether, benzyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, etc., benzoin alkyl ethers or esters, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-monoacylphosphine oxide, bisacylphosphine oxide or titanocene, fluorescein, anthraquinone, thioxanthone or xanthone, lophine dimer, trihalomethyl compound or dihalomethyl compound, active ester compound, organoboron compound, etc., but are not limited thereto.

[0228] In addition, a photo-crosslinkable radical generator such as a diazo compound can also be contained. Further, in the case of polymerization only by heat, a usual thermal polymerization initiator such as azobisisobutyronitrile (AIBN), which is a usual photo radical generator, can be used.

[0229] From the viewpoint of obtaining a sufficient curing rate, the content of the polymerization initiator is preferably 0.05% by mass or more and 10.0% by mass or less, more preferably 0.5% by mass or more and 5.0% by mass or less, based on 100.0% by mass of the total mass of the polymerizable compounds.

[0230] The liquid composition can be a non-dispersed composition without a dispersion in the liquid composition, or a dispersed composition with a dispersion in the liquid composition, but a non-dispersed composition is preferred.

[0231] [Polymerization-induced phase separation]

[0232] A porous resin is formed by polymerization-induced phase separation. Polymerization-induced phase separation refers to a state where a polymerizable compound and a pore-forming agent are miscible, but the polymer (resin) generated during the polymerization of the polymerizable compound is immiscible with the pore-forming agent (phase separation occurs). Although there are other methods to obtain a porous body through phase separation, the method using polymerization-induced phase separation can form a porous body with a network-like structure. Therefore, a porous body with high chemical resistance and high heat resistance can be expected. Compared with other methods, the polymerization-induced phase separation method also has advantages such as a short process time and easy surface modification.

[0233] Next, the process of forming a porous resin by polymerization-induced phase separation using a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. At this time, since the solubility of the pore-forming agent in the growing resin decreases, phase separation occurs between the resin and the pore-forming agent. Eventually, the resin forms a porous structure in which pores are filled with a pore-forming agent or the like and have a co-continuous structure constructed by a resin skeleton. Then, the pore-forming agent or the like is removed by drying, leaving a porous resin with a co-continuous structure having a three-dimensional network-like structure. Therefore, in order to form a porous resin with an appropriate porosity, the miscibility between the pore-forming agent and the polymerizable compound and the miscibility between the pore-forming agent and the resin formed by the polymerization of the polymerizable compound have been studied.

[0234] [Transmittance]

[0235] The transmittance at a wavelength of 550 nm measured while stirring the liquid composition is 30% or more.

[0236] The miscibility between the pore-forming agent and the polymerizable compound can be determined by the transmittance.

[0237] When the transmittance is 30% or more, it is judged that there is a pore-forming agent in the liquid and the polymerizable compound is miscible with the pore-forming agent. When the transmittance is less than 30%, it is judged that the polymerizable compound is immiscible with the liquid.

[0238] The transmittance can be measured specifically by the following method.

[0239] First, inject the liquid composition into a quartz container, stir the liquid composition with a stirrer at 300 rpm, and simultaneously measure the transmittance of light (visible light) with a wavelength of 550 nm.

[0240] - Quartz container: A special micro-container with a nut (trade name: M25-UV-2, manufactured by GL Sciences).

[0241] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0242] - Stirring speed: 300 rpm.

[0243] - Measurement wavelength: 550 nm

[0244] - Reference: In the state where the inside of the quartz container is air, measure the transmittance of light with a wavelength of 550 nm (transmittance 100%).

[0245] [Haze value increase rate]

[0246] The increase rate of the haze value of the haze measurement element produced by polymerizing this liquid composition is 1.0% or more.

[0247] The compatibility between the pore-forming agent and the resin formed by the polymerization of the polymerizable compound can be judged by the increase rate of the haze value.

[0248] When the increase rate of the haze value is 1.0% or more, it is judged that there is a pore-forming agent in the liquid and the resin and the pore-forming agent are incompatible. When the increase rate of the haze value is less than 1.0%, it is judged that the resin and the liquid are compatible.

[0249] The lower the compatibility between the resin formed by the polymerization of the polymerizable compound and the pore-forming agent in the haze measurement element, the higher the haze value, and the higher the compatibility, the lower the haze value. In addition, the higher the haze value, the easier it is for the resin formed by the polymerization of the polymerizable compound to form a porous structure.

[0250] Specifically, the increase rate of the haze value refers to the increase rate of the haze value before and after polymerization of the haze measurement element with an average thickness of 100 μm produced by polymerizing the liquid composition, and can be measured by the following method.

[0251] - Fabrication of the haze measurement element -

[0252] First, resin microparticles are uniformly dispersed on an alkali-free glass substrate by spin coating to serve as a spacer. Next, the substrate coated with the spacer and an alkali-free glass substrate without the spacer coating are bonded to each other in a manner that sandwiches the surface coated with the spacer. Then, the liquid composition Z is filled between the bonded substrates by capillary action to fabricate an "element for measuring haze before UV irradiation". Next, the element for measuring haze before UV irradiation is irradiated with UV light to cure the liquid composition. Finally, the periphery of the substrate is encapsulated with a sealant to fabricate a "haze measurement element". The size of the spacer (average particle diameter: 100 μm) corresponds to the average thickness of the haze measurement element. Hereinafter, each condition during fabrication will be described.

[0253] - Alkali-free glass substrate: OA-10G manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t = 0.7 mm.

[0254] - Spacer: Resin microparticles MICROPEARL GS-L100, average particle diameter of 100 μm, manufactured by Sekisui Chemical Co., Ltd.

[0255] - Spin coating conditions: Amount of dispersion droplet added: 150 μL, rotation speed: 1000 rpm, rotation time: 30 s.

[0256] - Amount of liquid composition filled: 160 μL

[0257] - UV irradiation conditions: Using a UV-LED as the light source, light source wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s.

[0258] - Sealant: TB3035B (manufactured by Three Bond Co., Ltd.)

[0259] - Measurement of haze value (blur) -

[0260] Next, the haze value (blur) is measured using the fabricated element for measuring haze before UV irradiation and the haze measurement element. Taking the measured value of the element for measuring haze before UV irradiation as the reference (haze value 0), the increase rate of the measured value (haze value) of the haze measurement element relative to the measured value of the element for measuring haze before UV irradiation is calculated.

[0261] The apparatus used for measurement is as follows:

[0262] - Haze meter: Hazemeter NDH5000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.

[0263] [Viscosity]

[0264] From the viewpoint of workability when applying the liquid composition, the viscosity of the liquid composition is preferably 1.0 mPa·s or more and 150.0 mPa·s or less at 25°C, more preferably 1.0 mPa·s or more and 30.0 mPa·s or less, and particularly preferably 1.0 mPa·s or more and 25.0 mPa·s or less. By providing a liquid composition having a viscosity of 1.0 mPa·s or more and 30.0 mPa·s or less, good dischargeability can also be obtained when the liquid composition is applied by an inkjet method. Its viscosity can be measured using, for example, a viscometer (product name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

[0265] [Hansen Solubility Parameter (HSP)]

[0266] The compatibility between the above-mentioned pore-forming agent and the polymerizable compound, and the compatibility between the pore-forming agent and the resin formed by polymerizing the polymerizable compound can be predicted by the Hansen solubility parameter (HSP).

[0267] The so-called Hansen solubility parameter (HSP) is a useful tool for predicting the compatibility of two substances and is a parameter discovered by Charles M. Hansen. The Hansen solubility parameter (HSP) is represented by a combination of the following three parameters (δD, δP, and δH) derived from experiments and theories. The unit of the Hansen solubility parameter (HSP) is MPa 0.5 or (J / Cm 3 ) 0.5 . In this embodiment, (J / cm 3 ) 0.5 is used.

[0268] -δD: Energy derived from London dispersion force.

[0269] -δP: Energy derived from dipole-dipole interaction.

[0270] -δH: Energy derived from hydrogen bond force.

[0271] The Hansen solubility parameter (HSP) is a vector expressed as (δD, δP, δH), which is plotted in a three-dimensional space (Hansen space) with these three parameters as the coordinate axes. For commonly used substances, the Hansen solubility parameters (HSP) are available from well-known information sources such as databases. Therefore, the Hansen solubility parameters (HSP) of the required substances can be obtained by referring to the database. For substances whose Hansen solubility parameters (HSP) are not registered in the database, the Hansen solubility parameters (HSP) can be calculated from the chemical structure of the substance and the Hansen solubility sphere method described below using computer software such as Hansen Solubility Parameters in Practice (HSP iP). The Hansen solubility parameter (HSP) of a mixture containing two or more substances is calculated by the following method: for the Hansen solubility parameters (HSP) of each substance, multiply by the volume ratio of each substance to the whole mixture, and then take the vector sum of the obtained values. In this embodiment, the Hansen solubility parameter (HSP) of a liquid obtained based on a well-known information source such as a database is referred to as the "Hansen solubility parameter of the liquid".

[0272] The relative energy difference (RED) based on the Hansen solubility parameter (HSP) of the solute and the Hansen solubility parameter (HSP) of the solution is expressed by the following formula:

[0273] [Equation 1]

[0274] Relative energy difference (RED) = Ra / Ro (Equation 1)

[0275] In the above formula, Ra represents the interaction distance between the Hansen solubility parameter (HSP) of the solute and the Hansen solubility parameter (HSP) of the solution, and Ro represents the interaction radius of the solute. The interaction distance Ra between the Hansen solubility parameters (HSP) represents the distance between two substances. The smaller this value is, the closer the two substances are in the three-dimensional space (Hansen space), indicating a higher possibility of mutual dissolution (miscibility).

[0276] Assuming that the respective Hansen solubility parameters (HSP) of two substances (solute A and solution B) are as follows, Ra can be calculated as follows:

[0277] -HSP A =(δD A , δP A , δH A )

[0278] -HSP B =(δD B , δP B , δH B )

[0279] -Ra = [4×(δD A -δD B ) 2 +(δP A -δP B ) 2 +(δH A -δH B ) 2 1 / 2

[0280] Ro (the interaction radius of the solute) can be determined by the Hansen solubility sphere method described below.

[0281] -Hansen solubility sphere method-

[0282] First, prepare the substance for which Ro is to be determined and dozens of evaluation liquids with known Hansen solubility parameters (HSPs) (liquids different in meaning from the above-mentioned "liquids (pore formers)"), and conduct a compatibility test of the target substance with each evaluation liquid. In the compatibility test, the Hansen solubility parameters (HSPs) of the evaluation liquids showing compatibility and those of the evaluation liquids not showing compatibility are plotted on the Hansen space respectively. Based on the plotted Hansen solubility parameters (HSPs) of each evaluation liquid, a hypothetical sphere (Hansen sphere) is created on the Hansen space. The hypothetical sphere includes the Hansen solubility parameters (HSPs) of the group of evaluation liquids showing compatibility and does not include the Hansen solubility parameters (HSPs) of the group of evaluation liquids not showing compatibility. The radius of the Hansen sphere is the interaction radius Ro of the substance, and the center is the Hansen solubility parameter (HSP) of the substance. The evaluation criterion (the criterion for judging whether it is compatible) for the compatibility between the substance for which the interaction radius Ro and the Hansen solubility parameter (HSP) are to be determined and the evaluation liquids with known Hansen solubility parameters (HSPs) is set by the evaluator himself / herself. The evaluation criterion of this embodiment will be described later.

[0283] -Hansen solubility parameter (HSP) and interaction radius of the polymerizable compound-

[0284] ​The Hansen solubility parameter (HSP) of the polymeric compound in this embodiment, and the interaction radius of the polymeric compound are determined by the Hansen solubility sphere method. As described above, the evaluation criterion for compatibility in the Hansen solubility sphere method is set by the evaluator himself / herself. Therefore, the Hansen solubility parameter (HSP) of the polymeric compound Z in this embodiment obtained according to the following criterion is expressed as "the Hansen solubility parameter C of the polymeric compound Z", and the interaction radius of the polymeric compound Z is expressed as "the interaction radius D of the polymeric compound Z". In other words, "the Hansen solubility parameter C of the polymeric compound Z" and "the interaction radius D of the polymeric compound Z" are different from the "Hansen solubility parameter of the solvent" obtained based on publicly known information sources such as databases, and are obtained based on the Hansen solubility sphere method including the compatibility evaluation criterion set by the evaluator himself / herself.

[0285] The Hansen solubility parameter C of the polymeric compound and the interaction radius D of the polymeric compound can be obtained from the compatibility evaluation of the polymeric compound with respect to the evaluation liquid for relative evaluation (evaluation based on "measuring the transmittance at a wavelength of 550 nm of the transmittance measurement composition containing the polymeric compound and the evaluation liquid while stirring") according to the following [1-1] and the above transmittance measurement method.

[0286] [1-1] Preparation of the transmittance measurement composition

[0287] First, prepare a polymeric compound for which the Hansen solubility parameter (HSP) is to be determined, and dozens of evaluation liquids with known Hansen solubility parameters (HSP). Mix the polymeric compound, each evaluation liquid, and a polymerization initiator at the ratios shown below to prepare a transmittance measurement composition. Dozens of evaluation liquids with known Hansen solubility parameters (HSP) use the following 21 evaluation liquids.

[0288] - Transmittance measurement composition ratio -

[0289] - Polymeric compound for which the Hansen solubility parameter (HSP) is to be determined: 28.0% by mass

[0290] - Evaluation liquid with known Hansen solubility parameter (HSP): 70.0% by mass

[0291] - Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass

[0292] - Evaluation liquid group (21 kinds) -

[0293] Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0294] - Hansen solubility parameter (HSP) and interaction radius of the resin formed by polymerization of a polymerizable compound

[0295] The Hansen solubility parameter (HSP) of the resin formed by polymerization of a polymerizable compound and the interaction radius of the resin formed by polymerization of a polymerizable compound are determined by the Hansen solubility sphere method. As described above, the evaluation criteria for the compatibility of the Hansen solubility sphere method are set by the evaluator himself / herself. Therefore, the Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound of the present invention obtained according to the following criteria is expressed as "Hansen solubility parameter A of the resin", and the interaction radius of the resin formed by polymerization of the polymerizable compound is expressed as "interaction radius B of the resin". In other words, "Hansen solubility parameter A of the resin" and "interaction radius B of resin Z" are different from the "Hansen solubility parameter of the liquid" obtained based on publicly known information sources such as databases, and are obtained based on the Hansen solubility sphere method including the compatibility evaluation criteria set by the evaluator himself / herself.

[0296] The Hansen solubility parameter A of the resin and the interaction radius B of the resin can be obtained from the compatibility evaluation of the resin with respect to the evaluation liquid (evaluation based on "the increase rate of the haze value (blurriness) of the haze measurement element made of the haze measurement composition containing the polymerizable compound and the evaluation liquid") according to the following [2-1] and the above-described method for measuring the increase rate of the haze value.

[0297] [2-1] Preparation of the haze measurement composition

[0298] First, prepare the precursor (polymerizable compound) of the resin for which the Hansen solubility parameter (HSP) is to be determined and dozens of evaluation liquids with known Hansen solubility parameters (HSP), and mix the polymerizable compound, each evaluation liquid, and a polymerization initiator at the following ratios to prepare a haze measurement composition. Dozens of evaluation liquids with known Hansen solubility parameters (HSP) use the following 21 evaluation liquids.

[0299] - Haze measurement composition ratio -

[0300] - Precursor of the resin (polymerizable compound) for which the Hansen solubility parameter (HSP) is to be determined: 28.0% by mass

[0301] - Liquids for known evaluation of Hansen solubility parameter (HSP): 70.0% by mass

[0302] - Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass

[0303] - Evaluation liquid group (21 kinds)-

[0304] Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0305] - Relative energy difference (RED) of Hansen solubility parameter (HSP) based on resin and liquid (porogen)-

[0306] As described above, a haze measurement element is produced using a haze measurement composition containing a polymerizable compound and an evaluation liquid, and the Hansen solubility parameter A of the resin polymerized from the polymerizable compound determined from the rate of increase in the haze value (blurriness) of the haze measurement element, the interaction radius B of the resin, and the Hansen solubility parameter of the porogen are used to calculate the relative energy difference (RED) according to the following formula 2. The relative energy difference (RED) is preferably 1.00 or higher, more preferably 1.10 or higher, still more preferably 1.20 or higher, and particularly preferably 1.30 or higher.

[0307] [Formula 2]

[0308] Relative energy difference (RED) =

[0309] (Distance between "Hansen solubility parameter A of resin" and "Hansen solubility parameter of solvent") / "Interaction radius B of resin" (Formula 2)

[0310] When the relative energy difference (RED) of the Hansen solubility parameter (HSP) based on the resin and the porogen is 1.00 or higher, phase separation easily occurs between the resin formed by polymerization of the polymerizable compound in the liquid composition and the porogen, and a porous resin is more easily formed, so it is very suitable.

[0311] - Relative energy difference (RED) of Hansen solubility parameter (HSP) based on polymerizable compound and liquid (porogen)-

[0312] As described above, while stirring the transmittance measurement composition containing the polymerizable compound and the evaluation liquid, the transmittance of the light with a wavelength of 550 nm of the transmittance measurement composition is measured. From the Hansen solubility parameter C of the polymerizable compound determined based on the transmittance of the above light, the interaction radius D of the polymerizable compound determined based on the compatibility between the polymerizable compound and the evaluation liquid, and the Hansen solubility parameter of the liquid, the relative energy difference (RED) is calculated according to the following formula 3. The relative energy difference (RED) is preferably 1.05 or lower, more preferably 0.90 or lower, still more preferably 0.80 or lower, and particularly preferably 0.70 or lower.

[0313] [Formula 3]

[0314] Relative energy difference (RED) =

[0315] (Distance between "Hansen solubility parameter C of the polymerizable compound" and "Hansen solubility parameter of the solvent") / "Interaction radius D of the polymerizable compound" (Formula 3)

[0316] When the relative energy difference (RED) based on the Hansen solubility parameters (HSP) of the polymerizable compound and the pore former is 1.05 or lower, the polymerizable compound and the pore former are likely to show compatibility, and the closer to 0, the better the compatibility. Therefore, by making the relative energy difference (RED) 1.05 or lower, a liquid composition can be obtained that exhibits high dissolution stability such that the polymerizable compound does not precipitate over time after being dissolved in the pore former. Due to the high solubility of the polymerizable compound in the pore former, the discharge stability of the liquid composition can be maintained. Therefore, the liquid composition of this example can be suitably applied to, for example, a method of ejecting a liquid composition, such as an inkjet method. In addition, when the relative energy difference (RED) is 1.05 or lower, the separation between the polymerizable compound and the pore former is suppressed in the state of the liquid composition before the start of the polymerization reaction, and the formation of irregular or non-uniform porous resins is suppressed.

[0317] [Method for manufacturing a liquid composition]

[0318] As a method for manufacturing the liquid composition, there is no particular limitation, and it can be appropriately selected according to the purpose. It is preferably prepared through steps such as dissolving a polymerization initiator in the polymerizable compound, further dissolving a pore former and other components, and stirring to form a uniform solution.

[0319] 《Storage container》

[0320] The storage container is a storage container that contains the liquid composition and a container, and the liquid composition is stored in the container.

[0321] As the above-mentioned container, it includes but is not limited to glass bottles, plastic containers, plastic bottles, stainless steel bottles, metal cans with a capacity of 18 liters, cylindrical cans, etc.

[0322] "Applying treatment, applying part"

[0323] The applying treatment is a treatment for applying the liquid composition stored in the storage container onto a substrate, and can be appropriately implemented by an applying part.

[0324] The discharging part is the part for applying the liquid composition onto a substrate.

[0325] As the above-mentioned applying treatment and applying part, as long as the liquid composition can be applied, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, any printing device corresponding to various printing methods such as spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slot coating method, capillary coating method, spraying method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. can be used. Among them, the inkjet printing method is preferred.

[0326] "Polymerization treatment, polymerization part"

[0327] The polymerization treatment is a treatment for polymerizing the liquid composition by applying heat or light, and can be appropriately implemented by a polymerization part.

[0328] The polymerization part is the part for polymerizing the liquid composition by applying heat or light.

[0329] Through the polymerization, the polymer compound in the liquid composition polymerizes, and through polymerization-induced phase separation, a porous resin is formed, and a laminate having a substrate and a porous resin on the substrate can be manufactured.

[0330] As the above-mentioned polymerization treatment and polymerization part, there is no particular limitation, and it can be appropriately selected according to the purpose such as the polymerization initiator used or the polymerization method. For example, in the case of photopolymerization, a light irradiation treatment and a light irradiation method of irradiating ultraviolet light with a wavelength of 365 nm for 3 seconds can be cited, and in the case of thermal polymerization, a heat treatment and a heating method of heating at 150 °C under vacuum drying for 12 hours can be cited, etc.

[0331] "Other treatments, other parts"

[0332] As other treatments in the manufacturing device of the above-mentioned laminate, as long as the effects of the present invention are not impaired, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, a removal treatment, etc. can be cited.

[0333] As other parts in the manufacturing method of the above laminate, as long as the effects of the present invention are not impaired, there are no particular limitations, and they can be appropriately selected according to the purpose. For example, a removal part etc. can be cited.

[0334] <<<Removal treatment, removal part>>>

[0335] The removal treatment is a treatment for removing a liquid from a porous resin formed by polymerizing a liquid composition through the polymerization treatment, and can be suitably carried out by a removal part.

[0336] The removal part is a part for removing a liquid from a porous resin formed by polymerizing a liquid composition in the polymerization part.

[0337] As a method for removing the above liquid, there are no particular limitations. For example, a method of removing a liquid such as a solvent or a dispersion liquid from a porous resin by heating can be cited. At this time, by heating under reduced pressure, the removal of the liquid can be further promoted, and the liquid remaining in the formed insulating layer can be suppressed, so it is preferred.

[0338] <Lamination process and lamination unit>

[0339] The lamination process is a process of laminating the first base material formed with the first adhesive porous insulating layer and the second base material in such a manner that the first adhesive porous insulating layer faces the second base material, and can be suitably carried out by a lamination unit.

[0340] The lamination unit is a unit for laminating the first base material formed with the first adhesive porous insulating layer and the second base material in such a manner that the first adhesive porous insulating layer faces the second base material.

[0341] It can be a mode where the above first base material is an electrode and the above second base material is a separator, or a mode where the above first base material is an electrode and the above second base material is an electrode. Any of the two modes can be preferably adopted. As an electrode for forming an adhesive porous insulating layer, it can be on an electrode substrate or on an electrode composite material layer provided on the electrode substrate.

[0342] <Bonding process and bonding unit>

[0343] The bonding process is a process of bonding the laminated first base material and second base material through the first adhesive porous insulating layer, and can be suitably carried out by a bonding unit.

[0344] The bonding unit is a unit for bonding the laminated first base material and second base material through the first adhesive porous insulating layer.

[0345] As the above-mentioned bonding method, a method of performing thermal bonding under the conditions of a temperature of 50°C or higher and 300°C or lower, a cylinder thrust of 50 N or higher and 1000 N or lower, and a time of 0.5 second or higher and 10 seconds or lower can be cited.

[0346] As the above-mentioned bonding method, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, a hot plate sealer (manufactured by Ishizaki Electric Co., Ltd.) etc. can be cited.

[0347] [Embodiment of forming a contact porous insulating layer or a laminate by directly applying a liquid composition to a substrate]

[0348] Figure 17 It is a schematic diagram showing an example of a manufacturing apparatus (liquid discharging apparatus) of a porous insulating layer for bonding for a component for an electrochemical element for realizing the present embodiment and a manufacturing method of a laminate.

[0349] A manufacturing apparatus 500 of a porous insulating layer for bonding is an apparatus for manufacturing a porous insulating layer for bonding using the above-mentioned liquid composition. The manufacturing apparatus of the porous insulating layer for bonding includes: a printing unit 100 that performs an application process of applying a liquid composition onto a printing substrate 4 to form a liquid composition layer; a polymerization unit 200 that performs a polymerization process of applying heat or light to the liquid composition layer to polymerize it; and a removal unit 300 that performs a removal process of removing a solvent in pores of a porous resin precursor 6 by heating the porous resin precursor 6 to obtain a porous resin. The manufacturing apparatus of the porous insulating layer for bonding includes a conveyance unit 5 that conveys the printing substrate 4, and the conveyance unit 5 conveys the printing substrate 4 at a preset speed in the order of the printing unit 100, the polymerization unit 200, and the heating unit 300.

[0350] -Printing unit 100-

[0351] The printing unit 100 includes: a printing apparatus 1a as an example of an application unit that realizes an application process of applying a liquid composition for forming a porous insulating layer for bonding onto a printing substrate 4; a storage container 1b that stores the liquid composition; and a supply pipe 1c that supplies the liquid composition stored in the storage container 1b to the printing apparatus 1a.

[0352] The storage container 1b stores the liquid composition 7, and the printing unit 100 discharges the liquid composition 7 from the printing apparatus 1a, applies the liquid composition 7 onto the printing substrate 4, and forms the liquid composition layer into a thin film shape. The storage container 1b may have a structure integrated with the manufacturing apparatus of the laminate, or may have a structure that can be detached from the manufacturing apparatus of the laminate. In addition, it may be a container for adding to a storage container integrated with the manufacturing apparatus of the laminate or a storage container that can be detached from the manufacturing apparatus of the laminate.

[0353] The storage container 1b and the supply pipe 1c can be arbitrarily selected as long as they can stably store and supply the liquid composition 7. The materials constituting the storage container 1b and the supply pipe 1c are preferably light-shielding in the short wavelength region of ultraviolet light and visible light. Thereby, the liquid composition 7 is prevented from starting to polymerize due to external light.

[0354] - Polymerization section 200 -

[0355] As Figure 17 shown, in the case of photopolymerization, the polymerization section 200 has a light irradiation device 2a as an example of a polymerization unit for carrying out the polymerization process and a polymerization inert gas circulation device 2b for circulating the polymerization inert gas. The light irradiation device 2a irradiates light on the liquid composition layer formed by the printing section 100 in the presence of the polymerization inert gas to cause photopolymerization thereof, thereby obtaining the porous resin precursor 6.

[0356] The light irradiation device 2a is appropriately selected according to the absorption wavelength of the photoinitiator contained in the liquid composition layer, and is not particularly limited as long as it is a device capable of initiating and carrying out the polymerization of the compound in the liquid composition layer. For example, ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs can be cited. However, since light having a short wavelength generally has a tendency to easily reach the deep part, it is preferable to select the light source according to the thickness of the formed porous membrane.

[0357] Next, regarding the irradiation intensity of the light source of the light irradiation device 2a, if the irradiation intensity is too strong, polymerization occurs rapidly before sufficient phase separation, so there is a tendency that it is difficult to obtain a porous structure. On the other hand, when the irradiation intensity is too weak, phase separation proceeds to a micron level or more, and it is easy to cause non-uniformity or coarsening of the pores. In addition, the irradiation time also becomes longer, and there is a tendency for productivity to decrease. Therefore, as the irradiation intensity, it is preferably 10 mW / cm 2 or higher and 1 W / cm 2 or lower, and more preferably 30 mW / cm 2 or higher and 300 mW / cm 2 or lower.

[0358] The polymerization inert gas circulation device 2b plays the following role: reducing the concentration of polymerizable oxygen contained in the atmosphere, not hindering the polymerization reaction of the polymerizable compound near the surface of the liquid composition layer, and enabling it to proceed. Therefore, as long as the polymerization inert gas used satisfies the above functions, there is no particular limitation, and specific examples thereof include, but are not limited to, nitrogen, carbon dioxide gas, and argon.

[0359] Regarding the O 2 concentration of the polymerization inert gas, considering that the effect of reducing hindrance can be effectively obtained, the O 2The concentration is less than 20% (an environment with a lower concentration than atmospheric oxygen concentration), more preferably 0% or higher and 15% or lower, and even more preferably 0% or higher and 5% or lower. Further, in order to achieve stable polymerization conditions, the polymerization inert gas circulation device 2b preferably has a temperature control unit capable of adjusting the temperature.

[0360] In the case of thermal polymerization, the polymerization section 200 may also be a heating device. There is no particular limitation on the heating device, and it can be appropriately selected according to the purpose. For example, substrate heating (such as a hot plate), an IR heater, a hot air heater, etc. can be cited, or they can be combined.

[0361] In addition, regarding the conditions of heating temperature, time, or light irradiation, they can be appropriately selected according to the polymerizable compound contained in the liquid composition 7 and the film thickness to be formed.

[0362] -Removing section 300-

[0363] As Figure 17 shown, the removing section 300 has a heating device 3a and performs a liquid removing process, that is, the porous resin precursor 6 formed by the polymerization section 200 is heated by the heating device 3a to dry and remove the remaining liquid. Thus, a porous resin can be formed. The removing section 300 can also perform the liquid removing under reduced pressure.

[0364] The removing section 300 also performs a polymerization promoting process and an initiator removing process. In the polymerization promoting process, the porous film precursor 6 is heated by the heating device 3a to further promote the polymerization reaction carried out in the polymerization section 200; in the initiator removing process, the photopolymerization initiator remaining in the porous film precursor 6 is dried and removed by heating with the heating device 3a. These polymerization promoting process and initiator removing process may not be carried out simultaneously with the liquid removing process, but can be carried out before or after the liquid removing process.

[0365] After the liquid removing process, the removing section 300 performs a polymerization completion process of heating the porous material under reduced pressure. The heating device 3a only needs to satisfy the above functions and there is no particular limitation. For example, an IR heater or a hot air heater can be cited.

[0366] In addition, regarding the heating temperature and time, they can be appropriately selected according to the boiling point of the liquid contained in the porous film precursor 6 and the film thickness to be formed.

[0367] In addition, as Figure 18 shown, Figure 17 the manufacturing device of the adhesive porous insulating layer may also have an additional printing section 100'. Figure 18The manufacturing apparatus for the adhesive porous insulating layer has, in addition to the printing unit 100 for applying the liquid composition for forming the adhesive porous insulating layer onto the printing substrate 4, an additional printing unit 100' for applying the liquid composition for forming the porous insulating layer onto the printing substrate 4. By applying different liquid compositions to multiple regions on the printing substrate 4 and then passing through the polymerization unit 200 and the removal unit 300, an adhesive porous insulating layer and a porous insulating layer can be formed respectively.

[0368] Figure 19 FIG. is a schematic diagram showing another example of the manufacturing apparatus (liquid discharging apparatus) for the adhesive porous insulating layer for realizing the manufacturing method of the adhesive porous insulating layer-imparting material or laminate for the electrochemical element component of the present embodiment.

[0369] The liquid discharging apparatus 300' can circulate the liquid composition in the liquid discharging head 306, the tank 307, and the tube 308 by controlling the pump 310 and the valves 311, 312.

[0370] In addition, the liquid discharging apparatus 300' is provided with an external tank 313, and when the liquid composition in the tank 307 decreases, the liquid composition can also be supplied from the external tank 313 to the tank 307 by controlling the pump 310 and the valves 311, 312, 314.

[0371] When using the apparatus for manufacturing the adhesive porous insulating layer, the liquid composition can be discharged to the target position on the object to be imparted.

[0372] Figure 20 FIG. shows another example of the manufacturing method of the adhesive porous insulating layer or laminate of the present embodiment.

[0373] The manufacturing method of the imparting material 210 of the adhesive porous resin imparted onto the substrate includes the step of sequentially discharging the liquid composition 12A onto the substrate 211 using the liquid discharging apparatus 300'.

[0374] First, a long and narrow substrate 211 is prepared. Then, the substrate 211 is wound around a cylindrical core to form the adhesive porous resin 212, and this side becomes the upper side in Figure 20 and is set on the feeding roller 304 and the winding roller 305. Here, the feeding roller 304 and the winding roller 305 rotate counterclockwise, and the substrate 211 is conveyed in the Figure 20 from right to left direction. Then, in the same manner as in FIG. 16, droplets of the liquid composition 12A are discharged from the liquid discharging head 306 above the substrate 211 between the feeding roller 304 and the winding roller 305 onto the sequentially conveyed substrate 211.

[0375] A plurality of liquid ejection heads 306 may also be provided in a direction substantially parallel to or substantially perpendicular to the conveyance direction of the substrate 211. Next, the substrate 211 onto which the liquid composition 12A has been ejected in the form of droplets is conveyed to the polymerization unit 309 by the feeding roller 304 and the take-up roller 305. As a result, the adhesive porous resin 212 is formed, and the article 210 provided with the adhesive porous resin on the substrate is obtained. Then, the article 210 provided with the adhesive porous resin is cut into a desired size by stamping or the like.

[0376] The polymerization unit 309 may be provided on either the upper or lower side of the substrate 211, or a plurality of polymerization units may be provided.

[0377] There is no particular limitation on the polymerization unit 309 as long as it does not directly contact the liquid composition 12A. In the case of thermal polymerization, examples thereof include a resistance heater, an infrared heater, and a hot air blower; in the case of photo-polymerization, examples thereof include an ultraviolet radiation device. A plurality of polymerization units 309 may also be provided.

[0378] There is no particular limitation on the conditions of heating or light irradiation, and they can be appropriately selected according to the purpose. By polymerization, the liquid composition 12A polymerizes to form an adhesive porous resin.

[0379] In addition, as Figure 21 shown, the can 307A can supply the liquid composition from the can 313A connected to the can 307A, and the liquid ejection head 306 may have a plurality of liquid ejection heads 306A and 306B.

[0380] [Embodiment of forming an adhesive porous insulating layer or laminate by indirectly applying a liquid composition to a substrate]

[0381] Figures 22 to 23 is a structural diagram showing an example of a printing unit that uses an inkjet method and a transfer method as an application unit of a manufacturing apparatus for an adhesive porous insulating layer according to the present embodiment, Figure 22 is a structural diagram showing a printing unit using a drum-shaped intermediate transfer body, Figure 23 is a structural diagram showing a printing unit using an endless belt-shaped intermediate transfer body.

[0382] Figure 22 The printing unit 400' shown transfers a liquid composition or a porous resin to a substrate through an intermediate transfer body 4001 to form a porous resin on the substrate, and is an inkjet printer.

[0383] The printing unit 400' includes an inkjet unit 420, a transfer drum 4000, a pretreatment unit 4002, an absorption unit 4003, a heating unit 4004, and a cleaning unit 4005.

[0384] The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The head 101 ejects a liquid composition onto the intermediate transfer member 4001 supported by the transfer drum 4000, thereby forming a liquid composition layer on the intermediate transfer member 4001. Each head 101 is a line head, and nozzles are arranged within the range of the width of the recording area that covers the maximum size of the substrate that can be used. The head 101 has a nozzle surface formed with nozzles below it, and the nozzle surface faces the surface of the intermediate transfer member 4001 with a minute gap therebetween. In the case of the present embodiment, since the intermediate transfer member 4001 has a structure that circulates and moves on a circular orbit, the plurality of heads 101 are arranged radially.

[0385] The transfer drum 4000 faces the impression cylinder 621 to form a transfer nip. Before the head 101 ejects the liquid composition, the pretreatment unit 4002, for example, imparts a reaction liquid for increasing the viscosity of the liquid composition to the intermediate transfer member 4001. The absorption unit 4003 absorbs the liquid component from the liquid composition layer on the intermediate transfer member 4001 before transfer. The heating unit 4004 heats the ink layer on the intermediate transfer member 4001 before transfer. By heating the liquid composition layer, the liquid composition thermally polymerizes to form a porous resin. In addition, the liquid is removed, and the transferability to the substrate is improved. The cleaning unit 4005 cleans the intermediate transfer member 4001 after transfer to remove foreign matters such as ink and dust remaining on the intermediate transfer member 4001.

[0386] The outer peripheral surface of the impression cylinder 621 is pressed against the intermediate transfer member 4001, and when the substrate passes through the transfer nip between the impression cylinder 621 and the intermediate transfer member 4001, the porous resin on the intermediate transfer member 4001 is transferred onto the substrate. In addition, the impression cylinder 621 may be configured to have at least one clamping mechanism on its outer peripheral surface for holding the front end portion of the substrate.

[0387] Figure 23 The illustrated printing unit 400″ is an inkjet printer that transfers a liquid composition or a porous resin onto a substrate through an intermediate transfer belt 4006, thereby forming a porous resin on the substrate.

[0388] The printing unit 400″ discharges droplets of the liquid composition from a plurality of heads 101 provided on the inkjet unit 420 to form a liquid composition layer on the outer peripheral surface of the intermediate transfer belt 4006. The liquid composition layer formed on the intermediate transfer belt 4006 is heated by the heating unit 4007 and thermally polymerized, thereby forming a porous resin and forming a film on the intermediate transfer belt 4006.

[0389] At the transfer nip where the intermediate transfer belt 4006 faces the transfer roller 622, the film-formed porous resin on the intermediate transfer belt 4006 is transferred onto the substrate. The surface of the intermediate transfer belt 4006 after transfer is cleaned by the cleaning roller 4008.

[0390] The intermediate transfer belt 4006 is mounted on the drive roller 4009a, the opposing roller 4009b, a plurality (four in this example) of shape-retaining rollers 4009c, 4009d, 4009e, and 4009f, and a plurality (four in this example) of support rollers 4009g, and moves in the direction of the arrow in the figure. The support roller 4009g disposed opposite to the head 101 maintains the stretched state of the intermediate transfer belt 4006 when ink droplets are discharged from the head 101.

[0391] [Use of a porous insulating layer imparting material for bonding parts for an electrochemical element and a laminate]

[0392] <Use for an electrochemical element>

[0393] As the use of the porous insulating layer imparting material for bonding parts for an electrochemical element and a laminate, there is no particular limitation, and it can be appropriately selected according to the purpose. However, it is preferable that the adhesive porous insulating layer is an adhesive porous insulating layer for bonding parts for an electrochemical element.

[0394] In the case of using as these uses, for example, it is preferable to form an insulating layer (separator) by applying a liquid composition onto an electrode composite layer previously formed on an electrode substrate as a base material.

[0395] When an electrode used in a power storage element such as a battery or a power generation element such as a fuel cell is used as a base material, if the adhesion between the insulating layer as a porous structure body and the base material is low, when the structure body is deformed by an external impact, when a foreign object such as a metal sheet penetrates, etc., an offset occurs between the porous structure body and the base material, and a short circuit may occur.

[0396] According to the porous insulating layer imparting material for bonding parts for an electrochemical element and a laminate of the present embodiment, an adhesive porous resin having adhesiveness and excellent flexibility and ion permeability of the insulating layer can be formed on the base material, the occurrence of layer lamination offset of the electrode can be reduced, and the occurrence of short circuits can be reduced.

[0397] As an insulating layer for an electrochemical element, for example, a film-like porous insulating layer having pores or a porosity of a specified size is known. On the other hand, in the case of using the above liquid composition, by appropriately adjusting the content of the polymerizable compound, the content of the pore-forming agent, the irradiation conditions of the active energy ray, etc., the pores or the porosity can be appropriately changed, and the design freedom in terms of the performance of the electrochemical element can be improved. In addition, since the liquid composition can be applied by various application methods, for example, the liquid composition can be applied by an inkjet method, and thus the design freedom in terms of the shape of the electrochemical element can be improved.

[0398] The insulating layer is a component that isolates the positive electrode and the negative electrode and ensures ionic conductivity between the positive electrode and the negative electrode. In addition, in the present disclosure, when expressed as an insulating layer, its shape is not limited to a layer shape.

[0399] The substrate may be an insulating layer (separator) for an electrochemical element or a porous insulating layer different from the adhesive porous insulating layer. By forming an adhesive porous resin on the porous insulating layer, various functions of the entire insulating layer, such as heat resistance, impact resistance, and high-temperature shrinkage resistance, can be increased or improved.

[0400] (Electrode)

[0401] The electrode according to an embodiment of the present invention includes an adhesive porous insulating layer imparting material of the component for an electrochemical element according to an embodiment of the present invention, the substrate includes an electrode substrate, and the adhesive porous insulating layer is provided as the outermost layer.

[0402] (Method for manufacturing an electrode and apparatus for manufacturing an electrode)

[0403] The method for manufacturing an electrode according to an embodiment of the present invention includes an adhesive porous insulating layer forming step of forming an adhesive porous insulating layer on a substrate having an electrode substrate, and may further include other steps as needed.

[0404] The apparatus for manufacturing an electrode according to an embodiment of the present invention includes an adhesive porous insulating layer forming unit for forming an adhesive porous insulating layer on a substrate having an electrode substrate, and may further include other units as needed.

[0405] The adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton. The resin is a crosslinked resin. In a peeling measurement method using a peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more. The peeling strength measurement element is obtained as follows: Prepare a substrate, which is one of two substrates each having a size of 30 mm × 100 mm. The adhesive porous insulating layer is disposed on one surface of each of the two substrates to provide the adhesive porous insulating layer, and the adhesive porous insulating layers are opposed to each other. Thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0406] Regarding the adhesive porous insulating layer forming step and unit, except that the substrate has an electrode substrate, the matters described in the adhesive porous insulating layer forming step in the method for manufacturing a laminate and the apparatus for manufacturing a laminate of the present invention can be appropriately selected.

[0407] (Electrode (first electrode and second electrode))

[0408] The electrode includes an electrode substrate and an adhesive porous insulating layer, and, if necessary, may further include at least one of an electrode composite layer or a porous insulating layer on the electrode substrate.

[0409] The negative electrode and the positive electrode are collectively referred to as the "electrode". The electrode substrate for the negative electrode and the electrode substrate for the positive electrode are collectively referred to as the "electrode substrate". The negative electrode composite layer and the positive electrode composite layer are collectively referred to as the "electrode composite layer".

[0410] When the first electrode is the negative electrode, the second electrode refers to the positive electrode. When the first electrode is the positive electrode, the second electrode refers to the negative electrode.

[0411] An electrode composite layer may be provided on the positive electrode and the negative electrode, but when the reaction occurs sufficiently inside the battery, the electrode composite layer may not be included.

[0412] In addition, in order to ensure battery characteristics, prevent short circuits, etc., a porous insulating layer other than the adhesive porous insulating layer may also be included.

[0413] <Electrode substrate>

[0414] The electrode substrate is not particularly limited as long as it is a conductive substrate. For example, aluminum foil, copper foil, stainless steel foil, titanium foil, an etched foil formed by etching these to have fine pores, and a porous electrode substrate that can be used for a lithium ion capacitor, etc. can be cited, but it is not limited to these. Such an electrode substrate can be preferably used for a secondary battery or a capacitor as a general power storage device, and is particularly preferably used for a lithium ion secondary battery.

[0415] In addition, a carbon paper or a fibrous electrode used in a power generation element such as a fuel cell that is non-woven or woven into a flat shape, and those having fine pores in the above-mentioned open-cell electrode substrate can also be used. Furthermore, in the case of a solar element, in addition to the above, those in which a transparent semiconductor film such as indium / titanium-based oxide or zinc oxide is formed on a flat substrate such as glass or plastic, and materials obtained by thinly vapor-depositing a conductive electrode film can also be used.

[0416] <Electrode composite layer>

[0417] The electrode composite layer (hereinafter referred to as the "active material layer") is not particularly limited and can be appropriately selected according to the purpose. For example, the electrode composite layer may contain an active material (negative electrode active material or positive electrode active material), and optionally a binder, a tackifier, a conductive agent, etc.

[0418] The negative electrode composite layer and the positive electrode composite layer are formed by dispersing a powdery active material, a binder, a conductive material, etc. in a liquid, coating and fixing the obtained liquid on the electrode substrate, and then drying. Spraying, dispenser, die coater, dip coating, etc. are usually used.

[0419] The electrode composite material layer is formed by dispersing powdery active materials, catalyst compositions, etc. in a liquid, coating and fixing the resulting liquid on an electrode substrate, and then drying. Spraying, dispenser, die coater, dip coating printing are usually used, and drying is performed after coating.

[0420] 《Active Material》

[0421] The positive electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions. Typically, a transition metal compound containing an alkali metal can be used as the positive electrode active material. As the transition metal compound containing an alkali metal, for example, as the lithium-containing transition metal compound, there is no particular limitation, and composite oxides containing at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium and lithium can be cited. As the composite oxide, there is no particular limitation, and for example, lithium-containing transition metal oxides such as lithium cobalt oxide, lithium nickel oxide, and lithium manganate, olivine salts such as LiFePO 4 etc., chalcogen compounds such as titanium disulfide and molybdenum disulfide, and manganese dioxide. The lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal acid oxide is replaced by a different element. As the different element, for example, Na, Mg, Se, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, etc. can be cited, but it is not limited thereto, and among them, Mn, Al, Co, Ni, and Mg are particularly preferred. The different element can be one kind, or two or more kinds. These positive electrode active materials can be used alone or in combination of two or more kinds. Examples of the above active materials in nickel-metal hydride batteries include, but are not limited to, nickel hydroxide.

[0422] The negative electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions. Typically, a carbon material containing graphite having a graphite crystal structure can be used as the negative electrode active material. As such a carbon material, natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), etc. can be cited. As materials other than carbon materials, lithium titanate can be cited. In addition, from the perspective of improving the energy density of lithium-ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as the negative electrode active material.

[0423] As the negative electrode active material in nickel-metal hydride batteries, for example, a hydrogen storage alloy can be cited. Specifically, AB2 type or A2B type hydrogen storage alloys can be cited.

[0424] 《Binder》

[0425] As the binder for the positive electrode or negative electrode, PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, methyl polyacrylate, ethyl polyacrylate, hexyl polyacrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropropylene, styrene-butadiene rubber, carboxymethyl cellulose, etc. can be used, but are not limited to these. Copolymers of two or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, hexadiene can also be used. In addition, two or more substances can be selected from them and used in combination. As the conductive agent contained in the electrode, there is no particular limitation, and for example, graphite-based materials such as natural graphite or artificial graphite, carbon black-based materials such as acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal carbon black, conductive fiber-based materials such as carbon fiber or metal fiber, metal powder-based materials such as carbon fluoride, aluminum, conductive whisker-based materials such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenyl derivatives, graphene derivatives can be used.

[0426] In a fuel cell, the active substance generally serves as a catalyst for the cathode electrode or anode electrode, and metal particles such as platinum, ruthenium, or platinum alloy are supported on a catalyst carrier such as carbon. In order to support the catalyst particles on the surface of the catalyst carrier, for example, the catalyst carrier is suspended in water, and a precursor of the catalyst particles (specific examples of the precursor include, but are not limited to, chloroplatinic acid, dinitrodiaminoplatinum, platinum chloride, platinum dichloride, bis(acetylacetonato)platinum, dichlorodiamineplatinum, dichlorotetraammineplatinum, chloroplatinous acid ruthenium chloride, chloroiridic acid, chlororhodic acid, ferrous chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, ferrous sulfate, copper chloride, etc. containing alloy components, etc.) is added and dissolved in the suspension, and an alkali is added to form metal hydroxide, and at the same time, a catalyst carrier is obtained, and the metal hydroxide is supported on the surface of the catalyst carrier. The catalyst carrier is coated on the electrode substrate and reduced in a hydrogen atmosphere or the like to obtain an electrode with catalyst particles (active substance) coated on the surface.

[0427] In the case of a solar cell, etc., in addition to tungsten oxide powder and titanium oxide powder, the active substance can also include SnO 2 , ZnO, ZrO 2 , Nb 2 O 5 , CeO 2 , SiO 2 , Al 2 O 3An oxide semiconductor layer such as this allows a pigment to be supported on the semiconductor layer. For example, compounds such as ruthenium-type transition metal complexes, ruthenium-bis-type transition metal complexes, osmium-type transition metal complexes, osmium-bis-type transition metal complexes, ruthenium-cis-diaquabipyridine complexes, phthalocyanines and porphyrins, and organic-inorganic perovskite crystals can be cited.

[0428] 《Conductive Agent》

[0429] As the conductive agent, for example, graphite-based materials such as natural graphite or artificial graphite, carbon black-based materials such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal carbon black, conductive fiber-based materials such as carbon fibers or metal fibers, metal powder-based materials such as carbon fluoride and aluminum, conductive whisker-based materials such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenyl derivatives and graphene derivatives can be used, but are not limited to these.

[0430] (Electrochemical Element)

[0431] The electrochemical element of the first embodiment of the present invention has a first electrode and a second electrode insulated from the first electrode. The first electrode and the second electrode form a laminate, and at least one of the first electrode and the second electrode is the electrode of the present invention described above.

[0432] The electrochemical element of the second embodiment of the present invention has the laminate of the present invention described above. The first substrate has an electrode substrate, and the second substrate has an electrode substrate.

[0433] The electrochemical element to which this embodiment can be applied is not particularly limited. Typical examples include, but are not limited to, secondary batteries and capacitors as power storage elements, and particularly preferred examples include, but are not limited to, lithium ion secondary batteries.

[0434] In addition, in the component for the electrochemical element of this embodiment, it is preferable that the first electrode is disposed outside the second electrode and bonded to the second electrode via the adhesive porous insulating layer. For example, the component for the electrochemical element has the following structure: a negative electrode is provided outside the positive electrode, the negative electrode and the positive electrode are laminated via an insulating layer, and are bonded via an adhesive porous insulating layer, and the negative electrode and the positive electrode are insulated by the insulating layer. The battery is formed of a component for the electrochemical element, an electrolyte injected into the component for the electrochemical element, and an outer package body that seals the component for the electrochemical element and the electrolyte.

[0435] <Electrolyte>

[0436] The electrolyte can be formed of an electrolytic solution or a solid electrolyte. When the electrolyte layer is an electrolytic solution, a non-aqueous electrolytic solution formed by dissolving an electrolyte salt in a non-aqueous solvent is preferable.

[0437] -Non-aqueous Solvent-

[0438] The non-aqueous solvent is preferably an aprotic organic solvent.

[0439] As the aprotic organic solvent, there is no particular limitation, and examples thereof include carbonate organic solvents, ester organic solvents, ether organic solvents, etc., and a low-viscosity solvent is preferred.

[0440] As the carbonate organic solvent, there is no particular limitation, and examples thereof include chain carbonates and cyclic carbonates. These substances can be used alone or in combination.

[0441] In particular, chain carbonates are preferred because of their high solubility of electrolyte salts.

[0442] Examples of the chain carbonate include, but are not limited to, dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). However, it is not limited to these. These substances can be used alone or in combination. Dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) are particularly preferred.

[0443] When using a mixed solvent obtained by combining dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC), the mixing ratio of dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) is not particularly limited and can be appropriately selected according to the purpose.

[0444] Examples of the cyclic carbonate include, but are not limited to, propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and fluoroethylene carbonate (FEC). These substances can be used alone or in combination. Propylene carbonate (PC) and ethylene carbonate (EC) are particularly preferred.

[0445] When using a mixed solvent obtained by combining ethylene carbonate (EC) as a cyclic carbonate and dimethyl carbonate (DMC) as a chain carbonate, the mixing ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is not particularly limited and can be appropriately selected according to the purpose.

[0446] As the ester organic solvent, there is no particular limitation, and examples thereof include cyclic esters and chain esters.

[0447] Examples of the cyclic ester include, but are not limited to, γ-butyrolactone (γ-BL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.

[0448] As the chain ester, there is no particular limitation, and examples thereof include, for example, alkyl propionates, dialkyl malonates, alkyl acetates, and alkyl formates.

[0449] Examples of the alkyl acetate include, but are not limited to, methyl acetate (MA) and ethyl acetate.

[0450] Examples of alkyl formates include, but are not limited to, methyl formate (MF) and ethyl formate.

[0451] As the ether organic solvent, there is no particular limitation, and cyclic ethers, chain ethers, etc. can be cited.

[0452] Examples of cyclic ethers include, but are not limited to, tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxane.

[0453] Examples of chain ethers include, but are not limited to, 1,2-dimethoxyethane (DME), ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether.

[0454] -Electrolyte salt-

[0455] As the electrolyte salt used in the non-aqueous electrolyte, a lithium salt is preferred.

[0456] There is no particular limitation on the lithium salt, and it can be appropriately selected according to the purpose as long as it is soluble in the non-aqueous solvent and exhibits high ionic conductivity. Examples thereof include, but are not limited to, lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium chloride (LiCl), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethylsulfonyl)imide salt (LiN(CF 3 SO 2 )) 2 ), lithium bis(pentafluoroethylsulfonyl)imide salt (LiN(C 2 F 5 SO 2 )) 2 ), lithium bis(fluorosulfonyl)imide salt (LiN(FSO 2 )) 2 ). These can be used alone or in combination. Among them, from the viewpoint of the amount of occlusion of the anion to the electrode, LiPF 6 , LiBF 4 , LiN(FSO 2 )) 2 are preferred.

[0457] The concentration of the electrolyte salt is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of balancing the discharge capacity and the output power, it is preferably 1.0 mol / L or more and 6 mol / L or less, more preferably 1.5 mol / L or more and 4 mol / L or less.

[0458] -Solid electrolyte-

[0459] Examples of solid electrolyte particles that can be used as the solid electrolyte include, but are not limited to, sulfide-based amorphous solid electrolyte particles, oxide-based amorphous solid electrolyte particles, and crystalline oxides.

[0460] (Manufacturing method and manufacturing apparatus of an electrochemical element)

[0461] The manufacturing method of the electrochemical element according to an embodiment of the present invention includes: an electrode manufacturing process of manufacturing an electrode by the manufacturing method of the electrode according to an embodiment of the present invention described above, and an element forming process of manufacturing an electrochemical element using the electrode, and may further include other appropriate processes as needed.

[0462] The manufacturing apparatus of the electrochemical element according to an embodiment of the present invention includes: an electrode manufacturing unit that manufactures an electrode by the manufacturing method of the electrode according to an embodiment of the present invention described above; an element forming unit that manufactures an electrochemical element using the electrode; and other units as needed.

[0463] <Electrode manufacturing process and electrode manufacturing unit>

[0464] The electrode manufacturing process can appropriately select the matters described in the manufacturing method of the electrode according to an embodiment of the present invention described above, and includes a process of forming an adhesive porous insulating layer, and may further include other processes such as an electrode processing process as needed.

[0465] The electrode manufacturing unit can appropriately select the matters described in the manufacturing apparatus of the electrode according to an embodiment of the present invention described above, and includes a unit for forming an adhesive porous insulating layer, and may further include other units such as an electrode processing unit as needed.

[0466] Through the above electrode manufacturing process and electrode manufacturing unit, an electrode having an electrode substrate and an adhesive porous insulating layer formed on the electrode substrate can be manufactured. The electrode may be a laminated electrode including an electrolyte layer, or an electrolyte layer integrated type laminated electrode in which an electrode composite layer provided on the electrode substrate and a porous resin are integrated.

[0467] Regarding the imparting process and imparting unit, the items described in the manufacturing method and manufacturing apparatus of the laminate can be appropriately selected.

[0468] Regarding the polymerization process and polymerization unit, the items described in the manufacturing apparatus and manufacturing method of the laminate can be appropriately selected.

[0469] <Element forming process and element forming section>

[0470] The element forming process is a process of manufacturing an electrochemical element using the above-mentioned laminated battery.

[0471] The element forming section is a unit for manufacturing an electrochemical element using a laminated battery.

[0472] The method of manufacturing an electrochemical element using a battery is not particularly limited, and a known method of manufacturing an electrochemical element can be appropriately selected. For example, at least one of the methods of providing a counter electrode, winding, laminating, and housing in a container can be cited, and a method of obtaining a power storage element, etc., but it is not limited thereto.

[0473] The element forming process does not need to include all the element forming processes, and may include a part of the element forming processes.

[0474] <Electrode processing process and electrode processing section>

[0475] The electrode processing section processes a laminated electrode formed with a resin layer downstream of the imparting section.

[0476] The electrode processing section can perform at least one of cutting, folding, or pasting. For example, the laminated electrode processing section can cut a laminated electrode formed with a resin layer to produce a laminate including the laminated electrode. The electrode processing section can wind or laminate a laminated electrode formed with a resin layer.

[0477] The electrode processing section has, for example, an electrode processing device for cutting, zigzag folding, laminating, and winding a laminated electrode formed with a porous resin layer according to a target battery form.

[0478] The electrode processing process performed by the electrode processing section is, for example, a process of processing a laminated electrode formed with a resin layer on the downstream side of the imparting process. The electrode processing process may include at least one of a cutting process, a folding process, or a pasting process.

[0479] [Examples]

[0480] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

[0481] <Preparation of liquid composition for resin formation>

[0482] Liquid compositions 1 to 4 for forming Resins 1 to 4 are prepared by mixing raw materials in the following proportions.

[0483] - Preparation of liquid composition 1 for forming Resin 1 -

[0484] A liquid composition 1 for forming Resin 1 (which is another porous resin) was prepared by mixing the following components in the following proportions: 29.0% by mass of tricyclodecane dimethanol diacrylate (EBECRYL 130, manufactured by Daicel-Allnex) as a polymerizable compound, 70.0% by mass of dipropylene glycol monomethyl ether (manufactured by Kanto Chemical) as a pore-forming agent, and 1.0% by mass of IRGACURE 184 (manufactured by BASF SE) as a polymerization initiator.

[0485] - Preparation of Liquid Composition 2 for Forming Resin 2 -

[0486] A liquid composition 2 for forming Resin 2 (which is an adhesive porous resin) was prepared by mixing the following components in the following proportions: 29.0% by mass of KAYARAD PEG400DA (manufactured by Nippon Kayaku) as a polymerizable compound, 70.0% by mass of methyl caprate (manufactured by Kanto Chemical) as a pore-forming agent, and 1.0% by mass of IRGACURE 819 (manufactured by BASF SE) as a polymerization initiator.

[0487] - Preparation of Liquid Composition 3 for Forming Resin 3 -

[0488] A liquid composition 3 for forming Resin 3 (which is a comparative thermoplastic resin) was prepared by mixing the following components in the following proportions: 29.0% by mass of W#9100 (manufactured by Kureha) as a thermoplastic resin, 70.0% by mass of NMP (manufactured by Mitsubishi Chemical) as a solvent, and 1.0% by mass of IRGACURE 819 (manufactured by BASF SE) as a polymerization initiator.

[0489] - Preparation of Liquid Composition 4 for Forming Resin 4 -

[0490] A liquid composition 4 for forming Resin 4 (which is an adhesive porous resin) was prepared by mixing the following components in the following proportions: 29.0% by mass of SR502 NS (ethoxylated (9) trimethylolpropane triacrylate, manufactured by Sartomer USA, LLC (now Arkema S.A.)) as a polymerizable compound, 70.0% by mass of methyl caprate (manufactured by Kanto Chemical) as a pore-forming agent, and 1.0% by mass of IRGACURE 819 (manufactured by BASF SE) as a polymerization initiator.

[0491] <Preparation of Liquid Composition for Forming Inorganic Solid Layer>

[0492] Mix the raw materials in the following proportions to prepare a predispersion, and disperse it in the following order to prepare a liquid composition for forming an inorganic solid layer.

[0493] - Liquid composition for forming an inorganic solid layer -

[0494] Mix 40.0% by mass of α-aluminum oxide (primary particle size (D50): 0.5 μm, specific surface area: 7.8 g / m 2 ), 58.0% by mass of a mixed solution of dimethyl sulfoxide and ethylene glycol (DMSO-EG, mass ratio 3:4), and 2.0% by mass of MALALILIM HKM-150A (manufactured by NOF Corporation) as a dispersant to prepare a predispersion. Put this predispersion together with zirconia beads (Φ2 mm) into a container, and disperse it in a freeze nanomill NP-100 (manufactured by Thinky Corporation) at 1500 rpm for 3 minutes to obtain a dispersion. Remove the zirconia beads from the obtained dispersion with a 25-μm screen filter to prepare a liquid composition for forming an inorganic solid layer.

[0495] <Preparation of the negative electrode>

[0496] - Preparation of the negative electrode coating -

[0497] Prepare a negative electrode coating by adding 97.0% by mass of graphite as a component for forming a negative electrode composite layer, 1.0% by mass of a thickener (carboxymethyl cellulose), 2.0% by mass of a polymer (styrene-butadiene rubber), and 100.0% by mass of water as a solvent.

[0498] - Preparation of the negative electrode -

[0499] As Figure 9 shown, coat the negative electrode coating on both sides (the area of the first electrode composite layer 9) of a copper foil substrate, and then dry it to form a negative electrode composite layer with a unit area weight of 9.0 mg / cm 2 . Then, press it in a roll press to provide an electrode with a bulk density of 1.6 g / cm 3 , thereby preparing a negative electrode. At this time, the average thickness of the negative electrode is 112.0 μm.

[0500] <Preparation of the positive electrode>

[0501] - Preparation of the positive electrode coating -

[0502] The positive electrode coating is prepared by dispersing 92.0% by mass of lithium nickel cobalt aluminum oxide (NCA) as a positive electrode active material, 3.0% by mass of acetylene black as a conductive material, and 5.0% by mass of polyvinylidene fluoride (PVDF) as a binder in N-methylpyrrolidone (NMP).

[0503] - Preparation of the positive electrode -

[0504] The positive electrode coating is applied to both sides of the aluminum foil substrate and dried to obtain a positive electrode composite layer with a unit area weight of 15.0 mg / cm2 on one side. Then, it is pressed in a roll press to provide an electrode with a bulk density of 2.8 g / cm3, thereby preparing the positive electrode. At this time, the average thickness of the positive electrode is 132.0 μm.

[0505] (Example 1)

[0506] <Manufacture of the negative electrode laminate>

[0507] As Figure 1 and Figure 2 shown, the liquid composition 1 for Resin 1 is filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (now Ricoh Industry Co., Ltd.)). The discharge amount of the liquid composition 1 discharged to the negative electrode composite layer of the negative electrode is controlled to form a coating area such that the average thickness of the porous insulating layer 10a is 20.0 μm.

[0508] Then, immediately in an N 2 atmosphere, it is irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) to irradiate the coating area and cure it. Then, it is heated on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, thereby obtaining the porous insulating layer 10a.

[0509] Subsequently, the liquid composition 2 for Resin 2 is filled into an inkjet discharge device equipped with a GEN5 head. Then, as Figure 1 and Figure 2 shown, the liquid composition 2 is discharged to the area shown in the adhesive porous insulating layer 10b to form a coating area with an average thickness of 100.0 μm. Then, immediately in an N 2 atmosphere, it is irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) to irradiate the coating area and cure it. After curing, it is heated on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, obtaining the adhesive porous insulating layer 10b.

[0510] In this way, as Figure 1 and Figure 2As shown, the negative electrode laminate of Example 1 was fabricated as the first electrode. In this first electrode, a porous insulating layer 10a was formed of resin 1 on the first electrode composite layer 9, and an adhesive porous insulating layer 10b was formed of resin 2 on three sides around the porous insulating layer 10a on the first electrode composite layer 9.

[0511] <Fabrication of Electrochemical Element>

[0512] As Figure 3 shown, the negative electrode having the porous insulating layer 10a and the adhesive porous insulating layer 10b formed thereon, which serves as the first electrode, was disposed opposite to and laminated with the positive electrode serving as the second electrode. The adhesive porous insulating layer 10b was thermally bonded for 1 second under a temperature of 140°C and a cylinder thrust of 500 N. Then, vacuum drying was performed at 150°C to remove the remaining water.

[0513] Then, an electrolytic solution was injected, and the laminated exterior material was used as the exterior for sealing to fabricate the electrochemical element (power storage element) of Example 1.

[0514] As the electrolytic solution, an electrolytic solution in which LiPF 6 , which serves as an electrolyte, was added to a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (a mixture with a mass ratio of EC:DMC = 1:1) so that its concentration was 1.5 mol / L was used.

[0515] <Evaluation>

[0516] The peel strength, flexibility, and ion permeability of the adhesive porous insulating layer were evaluated according to the following steps.

[0517] "Measurement of Peel Strength of Insulating Layer"

[0518] -Fabrication of Element for Measuring Peel Strength-

[0519] Liquid composition 1 was coated on one side of two electrodes each having a size of 30 mm × 100 mm and cured to fabricate two electrodes having the adhesive porous insulating layer 10b formed thereon. These two electrodes were used as test electrodes a and b. Then, the portions coated with the adhesive porous insulating layer 10b on the two electrodes were opposed to each other, and thermal bonding was performed for 1 minute under conditions of a temperature of 140°C and a cylinder thrust of 500 N to fabricate an "element for measuring peel strength".

[0520] The thickness of the adhesive porous insulating layer 10b was evaluated based on the thicknesses described in the examples and comparative examples.

[0521] -Measurement of Peel Strength-

[0522] The surface of the electrode substrate of the test electrode a of the element for measuring peel strength, which is opposite to the surface forming the adhesive porous insulating layer, is fixed to the specimen fixing surface of the peel strength measuring device with a thin double-sided tape. Then, the surface of the electrode substrate of the test electrode b of the element for measuring peel strength, which is opposite to the surface forming the adhesive porous insulating layer, is fixed to the tensile indenter of the peel strength measuring device with a tape. The peel strength is measured under the following measurement conditions.

[0523] - Measurement conditions for peel strength -

[0524] - Peel strength measuring device: Adhesion / Lamination Peel Analyzer Versatile Peel Analyzer (manufactured by Kyowa Interface Science Co., Ltd.)

[0525] - Thin double-sided tape: No. 5000NS (width 20 mm, manufactured by Nitto Denko Corporation)

[0526] - Tape: No. 29 (width 18 mm, manufactured by Nitto Denko Corporation)

[0527] - Measurement speed: 30 mm / min

[0528] - Peel angle: 90°

[0529] - Peel distance: 75 mm

[0530] "Evaluation of the flexibility of the insulating layer"

[0531] An electrode is fabricated in the same manner as the test electrode a used in the measurement of the peel strength of the insulating layer, cut into a square with a side length of 100 mm, and a bending test is performed using a cylindrical mandrel bending tester (manufactured by Kotec) equipped with a cylindrical mandrel with a diameter of φ4 mm. Then, it is observed whether cracks exist in the insulating layer before and after the bending test.

[0532] - Measurement conditions for flexibility -

[0533] Name of test equipment: Cylindrical mandrel bending test machine (manufactured by Kotec or Allgood)

[0534] - Necessary fixture: Mandrel with a diameter of 4 mm (same as above)

[0535] The presence or absence of cracks in the insulating layer is evaluated visually and using an optical microscope. The fewer cracks in the insulating layer, the better the bending property.

[0536] [Evaluation criteria]

[0537] Good: No cracks in the insulating layer.

[0538] Poor: Cracks exist in the insulating layer

[0539] "Evaluation of Ion Permeability of Insulating Layer"

[0540] The evaluation of the ion permeability of the insulating layer is carried out by observing the image with a scanning electron microscope (SEM) and measuring the porosity.

[0541] The adhesive porous insulating layer 10b was cut into a size of 5 mm × 10 mm and stained with osmium tetroxide (VIII) (manufactured by Nisshin EM Co., Ltd.). Specifically, the cut adhesive porous insulating layer was placed in a bottle containing a small amount of aqueous solution, without contacting the aqueous solution, and left standing in a sealed bottle for 30 minutes for staining. Then, the layer was dried in ventilation for 1 hour to provide a sample.

[0542] After sufficient drying, the sample was vacuum impregnated with a two-component epoxy resin (manufactured by ITW Performance Polymers Fluids Japan). Then, the cross-section was cut at 5.0 kV with a cross-section polisher (manufactured by JEOL Ltd.) and observed with cryoFIB / SEM (manufactured by FEI Company, Japan).

[0543] The porosity of the porous structure is calculated by binarizing the observed image and deriving the proportion of voids in the observed area.

[0544] The porosity of the adhesive porous insulating layer 11b is calculated by binarizing the observed image and obtaining the proportion of voids in the observed area. Based on the calculated porosity, the ion permeability is evaluated.

[0545] [Evaluation Criteria]

[0546] Good: Porosity is less than 30%

[0547] Poor: Porosity is 30% or more

[0548] (Example 2)

[0549] As Figure 1 and Figure 4 shown, the liquid composition for Resin 1 was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (now Ricoh Industry Co., Ltd.)). The amount of the liquid composition discharged onto the negative electrode composite layer of the negative electrode was controlled to form a coating area such that the film thickness of the porous insulating layer 11a was 20.0 μm.

[0550] Then, immediately in an N 2 atmosphere, it was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2, irradiate the coated area for 20 seconds and cure it. Then, heat it on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, thereby obtaining the porous insulating layer 10a.

[0551] Subsequently, the liquid composition for Resin 2 was filled into an inkjet discharging device equipped with a GEN5 head. The liquid composition was discharged onto the porous insulating layer 11a of the negative electrode of Resin 1 with a thickness of 20.0 μm. As Figure 1 and Figure 4 shown, a coated area with a film thickness of 65.0 μm was formed in the area shown by the adhesive porous insulating layer 10b. Then, immediately in N 2 atmosphere, irradiate the coated area with UV (light source: UV-LED (manufactured by Phoseon Technology, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cure it. After curing, heat it on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, and obtain the adhesive porous insulating layer 10b.

[0552] In this way, as Figure 4 shown, the negative electrode laminate of Example 2 was fabricated by sequentially laminating the first electrode substrate 8, the first electrode composite layer 9, the porous insulating layer 10a, and the adhesive porous insulating layer 10b. Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0553] An electrochemical element of Example 2 was fabricated in the same manner as in Example 1, except that the negative electrode laminate of Example 2 was used instead of the negative electrode laminate of Example 1.

[0554] (Example 3)

[0555] As Figure 7 and Figure 8 shown, the liquid composition for Resin 2 was filled into an inkjet discharging device equipped with a GEN5 head. The liquid composition was discharged onto the negative electrode active material in the area of the negative electrode excluding the separator, and a coated area with a patterned image and a film thickness of 90.0 μm was formed in the area shown by the adhesive porous insulating layer 10b. Then, immediately in N 2 atmosphere, irradiate the coated area with UV (light source: UV-LED (manufactured by Phoseon Techn o 1ogy, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cure it. After curing, heat it on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, and obtain the adhesive porous insulating layer 10b.

[0556] Next, on the negative electrode active material, inFigure 8 and Figure 10 A separator made of a polypropylene microporous membrane (manufactured by Toray Industries, Inc., SETELA (F20BHE), thickness 20 μm) is disposed in the region shown by the adhesive porous insulating layer 10b shown in Figure 10 .

[0557] (Example 4)

[0558] As Figure 1 and Figure 2 shown in Figure 1 and Figure 2 , a liquid composition for Resin 1 was filled into an inkjet discharging device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (now Ricoh Industry Co., Ltd.)). The discharge amount of the liquid composition discharged to the negative electrode composite material layer of the negative electrode was controlled to form a coating region, and the film thickness of the porous insulating layer 10a was made 20.0 μm.

[0559] Then, immediately in an N 2 atmosphere, the coating region was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 362 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. Then, it was heated on a hot plate at 130°C for 1 minute to remove the pore-forming agent, thereby obtaining the porous insulating layer 10a.

[0560] Subsequently, a liquid composition for Resin 4 was filled into an inkjet discharging device equipped with a GEN5 head. This liquid composition was discharged onto the porous insulating layer 10a of Resin 1 having a thickness of 20.0 μm formed on the negative electrode. As Figure 1 and Figure 4 shown in Figure 1 and Figure 4 , a coating region having a film thickness of 65.0 μm was formed in the region shown by the adhesive porous insulating layer 10b. Then, immediately in an N 2 atmosphere, the coating region was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 362 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. After curing, it was heated on a hot plate at 130°C for 1 minute to remove the pore-forming agent, obtaining the adhesive porous insulating layer 10b.

[0561] In this way, as Figure 3 shown in Figure 3 , the negative electrode laminate of Example 4 was fabricated by sequentially laminating the first electrode substrate 8, the first electrode composite material layer 9, the porous insulating layer 10a, and the adhesive porous insulating layer 10b. Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0562] An electrochemical element of Example 4 was produced in the same manner as in Example 1, except that the negative electrode laminate of Example 4 was used instead of the negative electrode laminate of Example 1.

[0563] (Comparative Example 1)

[0564] As Figure 1 and Figure 2 shown, the liquid composition for Resin 1 was filled into an inkjet discharging apparatus equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (currently Ricoh Industry Co., Ltd.)). The amount of the liquid composition discharged to the negative electrode active material of the negative electrode was controlled to form a coating area such that the film thickness of the porous insulating layer 10a was 20.0 μm.

[0565] Then, immediately under a N 2 atmosphere, the coating area was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. Subsequently, the coating area was heated on a hot plate at 130 °C for 1 minute to remove the pore former, thereby obtaining the porous insulating layer 10a.

[0566] Subsequently, the liquid composition for Resin 3 was filled into an inkjet discharging apparatus equipped with a GEN5 head. The liquid composition was discharged onto the negative electrode active material of the negative electrode, and as Figure 1 and Figure 2 shown, a coating area having a patterned image with a film thickness of 85.0 μm was formed in the area of the adhesive porous insulating layer 10b. Then, immediately under a N 2 atmosphere, the coating area was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. After curing, the coating area was heated on a hot plate at 130 °C for 1 minute to remove the solvent, thereby obtaining the adhesive porous insulating layer 10b formed of Resin 3 (thermoplastic resin).

[0567] Since the adhesive porous insulating layer 10b is formed of a thermoplastic resin, it loses its porosity by the heating for removing the solvent.

[0568] (Comparative Example 2)

[0569] As Figure 1 and Figure 2As shown, a liquid composition for Resin 1 was filled into an inkjet discharging device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (now Ricoh Industry Co., Ltd.)). The amount of the liquid composition discharged to the negative electrode active material of the negative electrode was controlled to form a coating area such that the film thickness of the porous insulating layer 11a was 20.0 μm.

[0570] Then, immediately in an N 2 atmosphere, the coating area was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. Subsequently, it was heated on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, thereby obtaining the porous insulating layer 10a.

[0571] Subsequently, a liquid composition for inorganic solids was filled into an inkjet discharging device equipped with a GEN5 head. The liquid composition was discharged onto the negative electrode active material of the negative electrode, and as Figure 1 and Figure 2 shown, a coating area with a pattern image having a film thickness of 85.0 μm was formed in the area shown by the adhesive porous insulating layer 10b. Then, immediately in an N 2 atmosphere, the coating area was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) and cured. Then, it was heated on a hot plate at 130 °C for 1 minute to remove the pore-forming agent, obtaining the adhesive porous insulating layer 10b formed of inorganic solids.

[0572] (Comparative Example 3)

[0573] As Figure 1 and Figure 2 shown, a liquid composition for Resin 1 was filled into an inkjet discharging device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd. (now Ricoh Industry Co., Ltd.)). The amount of the liquid composition discharged to the negative electrode active material of the negative electrode was controlled to form a coating area such that the film thickness of the porous insulating layer 11a was 20.0 μm.

[0574] Then, immediately in an N 2 atmosphere, the coating area was irradiated with UV (light source: UV-LED (manufactured by Phoseon Technology Co., Ltd., product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2, irradiate the coated area for 20 seconds) to cure it. Then, heat it at 130 °C for 1 minute using a hot plate to remove the pore-forming agent, thereby obtaining the porous insulating layer 10a.

[0575] Next, the liquid composition for Resin 1 is discharged onto the negative electrode active material of the negative electrode, as Figure 1 and Figure 2 shown, a coated area with a patterned image and a film thickness of 85.0 μm is formed in the area shown by the adhesive porous insulating layer 10b. Then, immediately in N 2 atmosphere, use UV (light source: UV-LED (manufactured by Phoseon Technology, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 seconds) to irradiate the coated area and cure it. After curing, heat it at 130 °C for 1 minute using a hot plate to remove the pore-forming agent, and obtain the adhesive porous insulating layer 10b formed of Resin 1. The glass transition temperature Tg of Resin 1 is 190 °C.

[0576] [Table 1]

[0577]

[0578] The results are shown in Table 1.

[0579] As shown in Comparative Example 3, when a firmly crosslinked material or a high-Tg resin (Resin 1) is used as the insulating layer 10b for bonding between the negative electrode composite material layers, this resin lacks flexibility. Therefore, although the strength is high, the flexibility of the insulating layer is low. Comparative Example 2 uses an inorganic solid layer, but the flexibility of the insulating layer 10b is also low. In addition, Comparative Example 1 using a thermoplastic resin (Resin 3) includes a chain-like molecular structure, and when heated, it melts and the pores collapse, so it almost loses ion permeability.

[0580] In contrast, according to Examples 1 to 4, by using a substrate and an adhesive porous insulating layer having a peel strength of 2 N / m or more disposed on the substrate, an electrochemical element with excellent flexibility and ion permeability of the insulating layer, less occurrence of layer lamination shift of the electrode, and good battery characteristics can be manufactured.

[0581] Aspects of the present invention are as follows:

[0582] <1>

[0583] A porous insulating layer imparting material for bonding components of an electrochemical element, the porous insulating layer imparting material comprising:

[0584] a substrate; and

[0585] An adhesive porous insulating layer on the substrate

[0586] The adhesive porous insulating layer is a porous structure having a co - continuous structure with a resin as a skeleton, and the resin is a cross - linked resin.

[0587] Among them, in the peeling measurement method using a peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more. The peeling strength measurement element is obtained as follows: Prepare a substrate. As one of two substrates each having a size of 30 mm × 100 mm, the adhesive porous insulating layer is disposed on the entire surface of one side of each of the two substrates to provide the adhesive porous insulating layer, and the adhesive porous insulating layers are opposed to each other. Thermal bonding is performed for 1 minute under the conditions of a temperature of 140 °C and a cylinder thrust of 500 N.

[0588] <2>

[0589] The porous insulating layer imparting material according to aspect <1>, wherein the resin is a polymer of a polymerizable compound that can be polymerized by energy irradiation.

[0590] <3>

[0591] The porous insulating layer imparting material according to aspect <2>, wherein the polymerizable compound has a (meth)acryloyl group.

[0592] <4>

[0593] A laminate, comprising:

[0594] The porous insulating layer imparting material according to any one of aspects <1> to <3>; and

[0595] Another substrate, which is bonded to the porous insulating layer imparting material through at least a part of the adhesive porous insulating layer.

[0596] <5>

[0597] An electrode, comprising:

[0598] The porous insulating layer imparting material according to any one of aspects <1> to <3>,

[0599] wherein the substrate has an electrode substrate, and the adhesive porous insulating layer is the outermost surface layer of the electrode.

[0600] <6>

[0601] An electrochemical element, comprising:

[0602] A first electrode; and

[0603] A second electrode insulated from the first electrode,

[0604] The first electrode and the second electrode together form a stack, and at least one of the first electrode and the second electrode is the electrode according to aspect <5>.

[0605] <7>

[0606] The electrochemical element according to aspect <6>, wherein at least a part of the adhesive porous insulating layer is adhered to the surface of another substrate.

[0607] <8>

[0608] The electrochemical element according to aspect <6> or <7>, wherein the first electrode is disposed outside the second electrode and adhered to the second electrode via the adhesive porous insulating layer.

[0609] <9>

[0610] The electrochemical element according to any one of aspects <6> to <8>, wherein the electrochemical element is a lithium ion secondary battery.

[0611] <10>

[0612] A laminate, comprising:

[0613] A first substrate; and

[0614] A second substrate,

[0615] The first substrate has a first adhesive porous insulating layer,

[0616] The first substrate and the second substrate are adhered via the first adhesive porous insulating layer,

[0617] The first adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, and the resin is a cross-linked resin,

[0618] Wherein, in the peeling measurement method using a peeling strength measurement element, the peeling strength of the first adhesive porous insulating layer is 2 N / m or more, and the peeling strength measurement element is obtained as follows: The first adhesive porous insulating layer is provided on the entire surface of one side of the first substrate having a size of 30 mm × 100 mm and on the entire surface of one side of the second substrate having a size of 30 mm × 100 mm, the first adhesive porous insulating layers are opposed to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0619] <11>

[0620] The laminate according to aspect <10>, wherein the second substrate has a second adhesive porous insulating layer, and the first substrate and the second substrate form the laminate such that the first adhesive porous insulating layer faces the second adhesive porous insulating layer.

[0621] <12>

[0622] The laminate according to aspect <10> or <11>, wherein the first substrate is an electrode and the second substrate is a separator.

[0623] <13>

[0624] The laminate according to aspect <10> or <11>, wherein the first substrate is an electrode and the second substrate is an electrode.

[0625] <14>

[0626] The laminate according to any one of aspects <10> to <13>, wherein the content of the binder in the first adhesive porous insulating layer is 0% by mass or more and 30% by mass or less.

[0627] <15>

[0628] A method for manufacturing a laminate, the method comprising:

[0629] a step of forming a first adhesive porous insulating layer on a first substrate;

[0630] a step of laminating the first substrate having the first adhesive porous insulating layer formed thereon and a second substrate such that the first adhesive porous insulating layer faces the second substrate; and

[0631] adhering the first substrate and the second substrate laminated in this way via the first adhesive porous insulating layer,

[0632] The first adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, and the resin is a crosslinked resin.

[0633] wherein, in a peel measurement method using a peel strength measurement element, the peel strength of the first adhesive porous insulating layer is 2 N / m or more, and the peel strength measurement element is obtained as follows: the first adhesive porous insulating layer is provided on the entire one surface of the first substrate having a size of 30 mm × 100 mm and on the entire one surface of the second substrate having a size of 30 mm × 100 mm, the first adhesive porous insulating layers are made to face each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0634] <16>

[0635] An electrochemical element, comprising:

[0636] The laminate according to any one of aspects <10> to <13>,

[0637] wherein the first substrate has an electrode substrate, and the second substrate has an electrode substrate.

[0638] <17>

[0639] A method for manufacturing an electrode, the method comprising:

[0640] A step of forming an adhesive porous insulating layer on a substrate having an electrode substrate,

[0641] The adhesive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, and the resin is a crosslinked resin,

[0642] wherein, in a peeling measurement method using a peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more, and the peeling strength measurement element is obtained as follows: Prepare a substrate, as one of two substrates each having a size of 30 mm × 100 mm, dispose the adhesive porous insulating layer over the entire surface of each substrate of the two substrates to provide the adhesive porous insulating layer, make the adhesive porous insulating layers face each other, and perform thermal bonding for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

[0643] <18>

[0644] A method for manufacturing an electrochemical element, the method comprising:

[0645] Manufacturing an electrode by the method according to aspect <17>; and

[0646] Manufacturing an electrochemical element using the electrode.

[0647] The porous insulating layer imparting material for bonding electrochemical element components according to any one of aspects <1> to <3>, the laminate according to any one of aspects <4>, <10> to <14>, the electrode according to aspect <5>, the electrochemical element according to any one of aspects <6> to <9>, <16>, the method for manufacturing a laminate according to aspect <15>, the method for manufacturing an electrode according to aspect <17>, and the method for manufacturing an electrochemical element according to aspect <18> can solve various conventional problems and achieve the object of the present invention.

[0648] The above embodiments are illustrative and do not limit the present invention. Therefore, many additional modifications and variations are possible in accordance with the above teachings. For example, within the scope of the present invention, elements and / or features of different illustrative embodiments may be combined with and / or replaced by each other. Any of the above operations may be performed in various other ways, for example, in an order different from the above order.

[0649] This application is based on Japanese Patent Application No. 2022-157940 filed with the Japan Patent Office on September 30, 2022, and claims the priority thereof. The entire contents of the above patent application are incorporated herein by reference.

[0650] List of Reference Numerals

[0651] 1a: Inkjet device

[0652] 1b: Ink container

[0653] 1c: Ink supply pipe

[0654] 2a: Light irradiation device

[0655] 2b: Polymerization inert gas flow device

[0656] 3a: Heating device

[0657] 4: First electrode

[0658] 5: Conveyor

[0659] 6: Porous membrane precursor

[0660] 7: Liquid composition

[0661] 8: First electrode substrate

[0662] 9: First electrode composite material layer

[0663] 10a: Porous insulating layer

[0664] 10b: Adhesive porous insulating layer

[0665] 11: Second electrode substrate

[0666] 12: Second electrode composite material layer

[0667] 13: Spacer

[0668] 100: Printing section (adhesive porous insulating layer liquid application unit)

[0669] 100′: Additional printing section (porous insulating layer liquid application unit)

[0670] 200: Polymerization section

[0671] 300: Removal section

[0672] 500: Manufacturing apparatus for adhesive porous insulating layer

Claims

1. A porous insulating layer imparting material for bonding components of an electrochemical element, the porous insulating layer imparting material comprises: a substrate; and a pressure-sensitive porous insulating layer on the substrate, the pressure-sensitive porous insulating layer being a porous structure having a co-continuous structure with a resin as a skeleton, the resin being a crosslinked resin, wherein, in a peeling measurement method using a peeling strength measurement element, the peeling strength of the pressure-sensitive porous insulating layer is 2 N / m or more, and the peeling strength measurement element is obtained as follows: Prepare a substrate, which is one of two substrates each having a size of 30 mm × 100 mm. The pressure-sensitive porous insulating layer is disposed on the entire surface of each of the two substrates to provide the pressure-sensitive porous insulating layer. The pressure-sensitive porous insulating layers are opposed to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

2. The porous insulating layer imparting material according to claim 1, wherein the resin is a polymer of a polymerizable compound that can be polymerized by energy irradiation.

3. The porous insulating layer imparting material according to claim 2, wherein the polymerizable compound has a (meth)acryloyl group.

4. A laminate, comprising: the porous insulating layer imparting material according to any one of claims 1 to 3; and another substrate, which is bonded to the porous insulating layer imparting material through at least a part of the pressure-sensitive porous insulating layer.

5. An electrode, comprising: the porous insulating layer imparting material according to any one of claims 1 to 3, wherein the substrate has an electrode substrate, and the pressure-sensitive porous insulating layer is the outermost surface layer of the electrode.

6. An electrochemical element, comprising: a first electrode; and a second electrode insulated from the first electrode, the first electrode and the second electrode form a laminate together, and at least one of the first electrode and the second electrode is the electrode according to claim 5.

7. The electrochemical element according to claim 6, wherein at least a part of the pressure-sensitive porous insulating layer is bonded to the surface of another substrate.

8. The electrochemical element according to claim 6 or 7, wherein the first electrode is disposed outside the second electrode and is bonded to the second electrode via the pressure-sensitive porous insulating layer.

9. The electrochemical element according to any one of claims 6 to 8, wherein the electrochemical element is a lithium ion secondary battery.

10. A laminate, comprising: a first substrate; and a second substrate, the first substrate has a first pressure-sensitive porous insulating layer, the first substrate and the second substrate are bonded via the first pressure-sensitive porous insulating layer, the first pressure-sensitive porous insulating layer is a porous structure having a co-continuous structure with a resin as a skeleton, the resin being a crosslinked resin, Among them, in the peeling measurement method using the peeling strength measurement element, the peeling strength of the first adhesive porous insulating layer is 2 N / m or more. The peeling strength measurement element is obtained as follows: The first adhesive porous insulating layer is provided on the entire one surface of the first substrate having a size of 30 mm × 100 mm and on the entire one surface of the second substrate having a size of 30 mm × 100 mm, and the first adhesive porous insulating layers are opposed to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

11. The laminate according to claim 10, wherein, the second substrate has a second adhesive porous insulating layer, and the first substrate and the second substrate together form the laminate such that the first adhesive porous insulating layer is opposed to the second adhesive porous insulating layer.

12. The laminate according to claim 10 or 11, wherein, the first substrate is an electrode and the second substrate is a separator.

13. The laminate according to claim 10 or 11, wherein, the first substrate is an electrode and the second substrate is an electrode.

14. The laminate according to any one of claims 10 to 13, wherein, the content of the adhesive in the first adhesive porous insulating layer is 0 mass% or more and 30 mass% or less.

15. A method for manufacturing a laminate, the method comprising: a step of forming a first adhesive porous insulating layer on a first substrate; a step of laminating the first substrate having the first adhesive porous insulating layer formed thereon and a second substrate such that the first adhesive porous insulating layer is opposed to the second substrate; and bonding the first substrate and the second substrate thus laminated via the first adhesive porous insulating layer, the first adhesive porous insulating layer being a porous structure body having a co-continuous structure with a resin as a skeleton, and the resin being a crosslinked resin, Among them, in the peeling measurement method using the peeling strength measurement element, the peeling strength of the first adhesive porous insulating layer is 2 N / m or more. The peeling strength measurement element is obtained as follows: The first adhesive porous insulating layer is provided on the entire one surface of the first substrate having a size of 30 mm × 100 mm and on the entire one surface of the second substrate having a size of 30 mm × 100 mm, and the first adhesive porous insulating layers are opposed to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

16. An electrochemical element, comprising: the laminate according to any one of claims 10 to 13, wherein the first substrate has an electrode substrate and the second substrate has an electrode substrate.

17. A method for manufacturing an electrode, the method comprising: a step of forming an adhesive porous insulating layer on a substrate having an electrode substrate, the adhesive porous insulating layer being a porous structure body having a co-continuous structure with a resin as a skeleton, and the resin being a crosslinked resin, Among them, in the peeling measurement method using the peeling strength measurement element, the peeling strength of the adhesive porous insulating layer is 2 N / m or more. The peeling strength measurement element is obtained as follows: Prepare a substrate. As one of two substrates each having a size of 30 mm × 100 mm, the adhesive porous insulating layer is disposed over the entire surface of each substrate of the two substrates to provide the adhesive porous insulating layer, the adhesive porous insulating layers are opposed to each other, and thermal bonding is performed for 1 minute under the conditions of a temperature of 140°C and a cylinder thrust of 500 N.

18. A method for manufacturing an electrochemical element, the method comprising: manufacturing an electrode by the method according to claim 17; and manufacturing an electrochemical element using the electrode.

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