Adhesive packaging material

Abstract

The present invention provides an adhesive package comprising a container and an adhesive composition for a secondary battery housed in the inner space of the container, the container comprising a housing part, a liquid delivery adapter provided so as to engage with an opening of the housing part, a liquid delivery tube, and a plug body, the liquid delivery adapter being provided so as to engage with the opening of the housing part, and the liquid delivery tube being provided so as to be inserted into the housing part. The top end of the liquid delivery tube is engaged with the liquid delivery adapter, the liquid delivery adapter and the liquid delivery tube constitute a liquid guide path that communicates an opening at the bottom end of the liquid delivery tube and the top side of the container, and the plug is detachably provided so as to be engaged with the liquid delivery adapter to seal the liquid guide path. The contact angle [theta] B between the adhesive composition and the inner wall surface of the container is 30 DEG or more.

Description

Technical Field

[0001] This invention relates to packaging for adhesives used in secondary batteries, and more particularly, to packaging for adhesives used in secondary batteries in a condition suitable for their storage and use. Background Technology

[0002] Binders are used as materials in the manufacture of batteries such as lithium-ion secondary batteries. Binders can be used as materials to bind the active material particles that make up the electrodes (positive or negative electrodes) in the battery, and as materials to bind layered structures such as electrodes and spacers together.

[0003] In most cases, adhesives are prepared as liquid adhesive compositions, such as slurries, which contain tiny particulate polymers that act as adhesives and a dispersion medium. The prepared adhesive compositions are sometimes used immediately after preparation, but in most cases, they are packaged in containers and stored until use.

[0004] Binders are substances that constitute the internal structure of batteries, and therefore their quality can have a significant impact on battery performance. Especially in the case of secondary batteries such as lithium-ion batteries, there is a requirement to improve performance while ensuring smooth charge and discharge, thus demanding high-quality binders. Therefore, the packaging of the binder composition must be able to preserve the binder composition without compromising its quality. Various packaging materials have been proposed to date as packaging for binder compositions (e.g., Patent Documents 1-3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2011-098736;

[0008] Patent Document 2: International Publication No. 2022 / 071523 (corresponding publication: U.S. Patent Application Publication No. 2023 / 331976);

[0009] Patent document 3: International Publication No. 2015 / 029835. Summary of the Invention

[0010] The problem the invention aims to solve

[0011] Compared to preparing and using the binder composition for secondary batteries immediately, storing the binder composition after preparation and then using it in battery manufacturing may result in poor coating of the binder composition and reduced battery performance. It is believed that such adverse effects are caused by the deterioration of the binder composition's quality due to storage, and that the packaging of the binder composition in the prior art cannot adequately suppress this quality deterioration.

[0012] Therefore, the object of the present invention is to provide a packaging for an adhesive composition that can suppress the deterioration of the quality of the adhesive composition due to storage, and allows for easy removal of the adhesive composition during use, and can effectively suppress the occurrence of defects in the resulting battery.

[0013] Solution for solving the problem

[0014] To address the aforementioned problems, the inventors conducted various studies. During these studies, they discovered that the deterioration of the binder composition's quality is significantly related to the introduction of coarse particles from the environment during the transfer of the binder composition from the container to the coating device, as well as the evaporation of the dispersion medium and the formation of agglomerates caused by contact between the binder composition and the container's inner wall during storage. The inventors further discovered that by using packaging materials specifically designed for the binder composition, the formation of particulate components such as coarse particles and agglomerates caused by these factors can be effectively suppressed, thus completing this invention.

[0015] That is, according to the present invention, the following solution is provided.

[0016] (1) An adhesive packaging comprising a container and an adhesive composition for a secondary battery housed within the internal space of the container, the container having a receiving portion, a liquid delivery adapter, a liquid delivery tube, and a plug, the receiving portion having an opening at its top, the liquid delivery adapter being configured to engage with the opening of the receiving portion, the bottom end of the liquid delivery tube being close to the bottom of the internal space of the container, and the top end engaging with the liquid delivery adapter, the liquid delivery adapter and the liquid delivery tube forming a liquid guiding path connecting the opening at the bottom end of the liquid delivery tube to the top side of the container, the plug being detachably configured to engage with the liquid delivery adapter to seal the liquid guiding path, and the contact angle θ between the adhesive composition and the inner wall surface of the container. B The temperature is above 30°.

[0017] (2) The adhesive packaging according to (1), wherein the liquid delivery adapter has a locking portion that can be connected to a connector for discharging the adhesive composition to the outside of the container.

[0018] (3) The adhesive packaging according to (1) or (2), wherein the adhesive composition comprises a particulate polymer having a glass transition temperature of 40°C or higher and 200°C or lower.

[0019] (4) The adhesive packaging according to (1) or (2), wherein the adhesive composition comprises a particulate polymer having a core-shell structure having a core and a shell covering the outer surface of the core, the glass transition temperature of the shell being 40°C or higher and 200°C or lower.

[0020] (5) The adhesive packaging according to (4), wherein the adhesive composition further comprises an auxiliary particulate polymer as a non-core-shell particulate polymer, and the proportion of the auxiliary particulate polymer in 100% by mass of the adhesive composition is 5% by mass or less.

[0021] (6) The adhesive packaging according to (1) or (2), wherein the adhesive composition comprises a particulate polymer, the particulate polymer being composed only of a particulate polymer having a core-shell structure having a core and a shell covering the outer surface of the core.

[0022] (7) An adhesive package according to any one of (1) to (6), wherein the adhesive composition comprises a particulate polymer, an anti-drying agent, and water, and the contact angle θ between the inner wall surface of the receiving portion and the water is [θ]. W It is above 80°.

[0023] (8) The adhesive packaging according to any one of (1) to (7), wherein the concentration of the particulate component with a ball volume equivalent diameter of 5 μm or more in the adhesive composition contained in the adhesive packaging, which has been stored for 6 months at an environment of 5°C or above and 40°C or below, is 1000 ppm or less.

[0024] Invention Effects

[0025] According to the present invention, a packaging for an adhesive composition can be provided that can suppress the deterioration of the quality of the adhesive composition due to storage, and can be easily removed during use, and can effectively suppress the occurrence of defects in the resulting battery. Attached Figure Description

[0026] Figure 1 A longitudinal sectional view is shown schematically as an example of a container that serves as an adhesive packaging material and a structural element thereof according to the present invention.

[0027] Figure 2A partial longitudinal sectional view schematically illustrating an example of the state in which the liquid delivery adapter and connector are connected for dispensing the adhesive composition from the adhesive package of the present invention. Detailed Implementation

[0028] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented in any way without departing from the scope of the claims and their equivalents. The structural elements of the embodiments shown below can be appropriately combined. Furthermore, the same symbols are used to denote the same structural elements in the figures, and their descriptions are sometimes omitted.

[0029] In the following description, "strip-shaped" substrate refers to a substrate having a length that is 5 times or more than its width, preferably 10 times or more, specifically a substrate with a length sufficient for winding into a roll for storage or handling. There is no particular upper limit to the length of the substrate, and it can be, for example, less than 100,000 times its width.

[0030] (Adhesive packaging: the shape of the container)

[0031] The adhesive packaging of the present invention has a container and an adhesive composition for secondary batteries housed therein.

[0032] Figure 1 A longitudinal sectional view is shown schematically as an example of a container, which is an adhesive packaging material and a structural element thereof according to the present invention. Figure 1 In the container 100, there is a receiving part 110, a liquid delivery adapter 120, a liquid delivery tube 130, and a plug 140. The receiving part 110 has an opening 111 at its top.

[0033] The liquid delivery adapter 120 is configured to engage with the opening 111 of the receiving portion 110. In this example, the liquid delivery adapter 120 and the receiving portion 110 are engaged with each other by a threaded portion 191 that engages with the external thread near the opening 111 of the receiving portion 110 and the internal thread of the corresponding portion of the liquid delivery adapter 120.

[0034] In this application, the engagement of the components constituting the container can be a sealing engagement that can block the inflow and outflow of fluid at the engagement portion. For example, the engagement between the receiving portion 110 and the liquid delivery adapter 120, the engagement between the liquid delivery adapter 120 and the liquid delivery pipe 130, the detachable engagement between the liquid delivery adapter 120 and the plug 140, and the engagement between the liquid delivery adapter 120 and the connector (described later) can all be sealing engagements that can block the inflow and outflow of fluid at the engagement portion. The engagement is not limited to detachable engagements; it can be either detachable or non-detachable engagements. Furthermore, the engagement of multiple components can be a mechanical engagement such as a screw connection, or it can be an integrated engagement utilizing the adhesion of multiple components, etc.

[0035] The liquid delivery adapter 120 has a through hole 121. The through hole 121 is a hole that connects its bottom side opening 121L to its top opening 121H. The bottom side opening 121L is an opening to the interior space 101 of the container, and the top opening 121H is an opening to the exterior of the container.

[0036] The liquid delivery tube 130 is a hollow tube with openings at both ends. The bottom end 131L of one end of the liquid delivery tube 130 is close to the bottom of the internal space 101 of the container 100. The top end 131H of the other end of the liquid delivery tube 130 engages with the bottom opening 121L of the liquid delivery adapter. Thus, the liquid delivery adapter 120 and the liquid delivery tube form a liquid guiding path connecting the opening of the bottom end 131L of the liquid delivery tube to the outside of the container.

[0037] The liquid delivery adapter 120 also has an air supply port 129, which is different from the through hole 121. The air supply port 129 is a hole that connects the bottom side opening 129L to the top side opening 129H.

[0038] The fluid delivery adapter 120 also has a connector engagement portion 123, including a recess 122, near its top side. The connector engagement portion 123 functions to engage the fluid delivery adapter 120 with a connector (described later).

[0039] The plug body 140 is detachably configured to engage with the liquid delivery adapter 120. In this example, the plug body 140 and the liquid delivery adapter 120 are screwed together by a threaded portion 192 that engages with the external thread near the top of the liquid delivery adapter 120 and the corresponding internal thread of the plug body 140, thus achieving a detachable engagement. Through this engagement, the plug body 140 seals the opening on its top side of the liquid delivery path (in this example, the top opening 121H of the liquid delivery adapter 120). Furthermore, through this engagement, the plug body 140 also seals the top opening 129H of the air supply port 129.

[0040] Figure 1The example container 100, by having this structure, enables the internal space 101 to become an airtight space. Thus, by storing a secondary battery adhesive composition as a liquid inside the container 100, the adhesive packaging of the present invention can be constructed.

[0041] When dispensing the adhesive composition from the adhesive packaging of the present invention for use, the plug is removed from the liquid delivery adapter and the connector is connected to the liquid delivery adapter.

[0042] Figure 2 A partial longitudinal sectional view schematically illustrating an example of the connection of the delivery adapter and connector for dispensing the adhesive composition from the adhesive packaging of the present invention. Figure 2 The text indicates the state after the plug 140 is removed from the liquid delivery adapter 120 of the adhesive packaging container 100, with the connector 150 connected to the liquid delivery adapter 120. The connecting portion 153 of the connector 150 has a shape that engages with the recess 122 of the connector engagement 123 of the liquid delivery adapter 120, thereby allowing easy connection by inserting the connector 150 into the liquid delivery adapter 120. In this example, the connector 150 has an open opening 151L at a position corresponding to the top opening 121H of the through hole 121, thereby allowing the adhesive composition flowing out from the liquid delivery path of the container 100 to be discharged into a device for using the adhesive composition. In this example, the adhesive composition can be discharged by pumping it upstream of the connector 150.

[0043] In this configuration, the container has a liquid delivery adapter that engages with the opening of the receiving section, and a liquid delivery tube that engages with the adapter. The bottom end of the delivery tube is close to the bottom of the container's internal space, and the top end engages with the adapter. This allows any adhesive composition remaining at the bottom of the container to be easily discharged outside the container when using the adhesive composition. Furthermore, by opening only the small opening at the top of the adapter without opening the receiving section and immediately sealing it with a connector, a connection to the connector for this discharge can be easily achieved. This significantly reduces the ingress of coarse particles from the environment when the adhesive composition is delivered from the container to the coating device. Therefore, by employing this structure, compared to conventional structures that open the container opening and insert the delivery tube from the outside for discharge, advantages are achieved in both ease of removing the adhesive composition and suppression of quality degradation of the adhesive composition.

[0044] Additionally, connector 150 has an open opening 159L at a position corresponding to the top opening 129H of the air supply port 129. This allows gas to be introduced into container 100 through opening 159L of connector 150. The gas introduced into container 100 through opening 159L can be a gas with a low concentration of coarse particles from the environment. For example, gas obtained by filtering outside air through a filter, or a gas with a low concentration of coarse particles pre-stored in a container, can be used. Such a gas with reduced coarse particle concentration can be a gas completely free of coarse particles, or a gas with a coarse particle concentration of 3000 particles / m² captured by a mesh filter with a 5 μm pore size. 3 The following gases.

[0045] (Contact Angle)

[0046] In the adhesive packaging of the present invention, the contact angle θ between the adhesive composition and the inner wall surface of the container is... B This is a large value above a specific threshold. The contact angle θ B The contact angle is 30° or higher, preferably 60° or higher. B There is no specific upper limit, and it can be less than 180°.

[0047] According to the inventor's discovery, by means of a contact angle θ having such a specific value B This significantly inhibits the degradation of the adhesive composition's quality during the storage of adhesive packaging. Unbound by any specific theory, this effect is believed to result from suppressing the aggregation of dispersions in the adhesive composition on the inner wall of the container. That is, during the storage of adhesive packaging, the adhesive composition is stored in the container's internal space at a level below a certain liquid level. Due to phenomena such as container shaking, a portion of this adhesive composition may sometimes adhere to the inner wall of the container at a level above this liquid level. At a contact angle θ... B In small cases, the adhesive composition adhering to the inner wall of the container remains attached for an extended period, causing partial evaporation of the dispersion medium and potentially leading to a localized increase in the concentration of dispersed particles (such as tiny particulate polymers) within the adhesive composition. In this situation, aggregation of the dispersed particles within the adhesive composition is likely to occur, resulting in aggregated particles. It is assumed that the contact angle θ... B At a specific high value, the aggregation of such dispersions is suppressed, and the formation of aggregate particles is inhibited.

[0048] Furthermore, it is believed that the inner wall of the container, positioned below the liquid level of the stored binder composition, interacts with the binder composition, thereby destabilizing the dispersion and allowing aggregation of the dispersed phase to occur, through the contact angle θ. B At specific high values, such instability is suppressed, and the generation of coarse molecules caused by condensation is suppressed.

[0049] Refer again Figure 1 To illustrate with an example, in container 100, since the adhesive composition contacts and is stored on the inner wall surface 102 of the storage section 100, the contact angle between the inner wall surface 102 of the storage section 100 and the adhesive composition is a large value greater than a specific value. Such a contact angle can be obtained by appropriately selecting a material that provides such a contact angle as the storage section 100 in relation to the adhesive composition. Specifically, when using an adhesive composition with water as the main dispersion medium, preferred examples of materials constituting the storage section 100 include high-density polyethylene (HDPE), polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyester, polyvinyl alcohol, etc.

[0050] Contact angle θ B It can also be modified by adjusting the components and proportions of the adhesive composition to an appropriate level. For example, the contact angle θ can be adjusted by appropriately regulating the proportions of components such as dispersants contained in the adhesive composition. B .

[0051] In the adhesive packaging of the present invention, the contact angle θ between water and the inner wall surface of the container is... W Preferably, it is a large value above a specific value. This contact angle θ W Preferably, the angle is 80° or more, more preferably 100° or more. Contact angle θ W There is no particular upper limit to the contact angle θ, which can be less than 180°. Various so-called aqueous adhesive compositions (i.e., adhesive compositions containing water as a dispersion medium) are known to have a contact angle θ. W This allows for the creation of an adhesive packaging that achieves the desired effects for any of the various water-based adhesive compositions using a common container.

[0052] (Adhesive composition)

[0053] The following describes the packaged adhesive composition, which is a structural element of the adhesive packaging of the present invention.

[0054] The binder composition is used as a material in the manufacture of secondary batteries such as lithium-ion secondary batteries. The binder composition can contain particulate polymers and a dispersion medium. From the viewpoint of ease of operation and reduction of environmental impact, a dispersion medium containing water is preferred as the dispersion medium. Furthermore, from the viewpoint of reducing the generation of agglomerated particles, the binder composition preferably contains an anti-drying agent.

[0055] In a preferred embodiment, the adhesive composition can be an adhesive composition comprising a particulate polymer, an anti-drying agent, and water, and in relation to the container, a contact angle θW The angle is above 80°. By adopting this structure, the ease of handling of the binder composition can be improved, the environmental impact of the binder composition during use can be reduced, the generation of agglomerate particles can be reduced, and the performance of the battery obtained from the binder composition can be improved.

[0056] In a preferred embodiment, the adhesive composition can be a coating liquid for inkjet coating. When using an inkjet coating liquid, there are problems such as nozzle clogging caused by particulate components like coarse particles and agglomerate particles contained in the coating liquid. The adhesive composition for packaging according to the present invention reduces such problems and is therefore particularly preferred.

[0057] In this application, the particulate component in the binder composition can be defined as a particulate component with a spherical volume equivalent diameter of 5 μm or more. The concentration of this particulate component in the binder composition can be determined by weighing the residue on the filter obtained by filtering the binder composition through a nylon mesh filter with a pore size of 5 μm. Such particulate components include particles generated by the aggregation of the dispersed phase in the binder composition, as well as foreign matter mixed in from the external environment during the operation of the binder composition. Therefore, in this application, particulate components with a spherical volume equivalent diameter of 5 μm or more are sometimes simply referred to as "particulate components," and particulate polymers and the like included as components of the binder composition are not included in the scope of "particulate components."

[0058] (Binder composition: particulate polymer)

[0059] Particulate polymers can function as materials for bonding active material particles that constitute the electrodes (positive or negative electrodes) within a battery, and as materials for bonding layered structures such as electrodes and spacers together. The binder composition may contain only one type of particulate polymer, or it may contain two or more types of particulate polymers.

[0060] The proportion of particulate polymer in the adhesive composition is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 15% by mass or less relative to the total adhesive composition.

[0061] If the proportion of particulate polymer is above the lower limit mentioned above, the adhesion between the electrode components of the secondary battery can be improved. On the other hand, if the proportion of particulate polymer is below the upper limit mentioned above, the inkjet ejection characteristics can be improved.

[0062] The particulate polymer preferably contains a polymer with a glass transition temperature of 40°C or higher. If the particulate polymer contains a polymer with a glass transition temperature of 40°C or higher, the inkjet ejection characteristics can be improved. Furthermore, when the glass transition temperature of the particulate polymer is high enough, the formation of agglomerates inside the container can be suppressed, resulting in a further enhancement of the contact angle θ as described above. B The effect obtained within a specific range. Preferably, at least a portion of the surface of the particulate polymer is composed of the aforementioned polymer.

[0063] Here, the glass transition temperature of the polymer is preferably 50°C or higher, more preferably 80°C or higher, more preferably 200°C or lower, and even more preferably 120°C or lower.

[0064] If the glass transition temperature of the polymer is above the lower limit mentioned above, the inkjet ejection characteristics can be further improved. On the other hand, if the glass transition temperature of the polymer is below the upper limit mentioned above, the particulate polymer softens moderately, so that an adhesive layer that can more firmly bond the battery components together can be formed even under pressure at room temperature.

[0065] The glass transition temperature of the polymer can be adjusted, for example, by changing the type and proportion of monomers used in the preparation of the polymer.

[0066] The volume average particle size of the particulate polymer is preferably 100 nm or more, more preferably 200 nm or more, even more preferably 400 nm or more, even more preferably 500 nm or more, preferably 1500 nm or less, more preferably 900 nm or less, even more preferably 800 nm or less, and even more preferably 700 nm or less.

[0067] By ensuring the volume average particle size of the particulate polymer is within the aforementioned range, the aggregation of the particulate polymer can be effectively suppressed, thereby improving the performance of the secondary battery obtained using the binder composition. Furthermore, if the volume average particle size of the particulate polymer is above or below the aforementioned lower limit, the deterioration of battery characteristics caused by the increase in secondary battery resistance due to obstruction of the electrode or spacer pathway can be suppressed. On the other hand, if the volume average particle size of the particulate polymer is below or below the aforementioned upper limit, nozzle clogging during inkjet coating of the binder composition can be further suppressed, thereby improving inkjet ejection characteristics.

[0068] In this specification, "volume-average particle size" refers to the particle size that accounts for 50% of the cumulative volume from the smallest diameter side in a volume-based particle size distribution determined by laser diffraction, and can be determined using the measurement methods described in the examples of this specification.

[0069] Particulate polymers can be particles composed of a single polymer or particles composed of multiple polymers (particles formed by the physical or chemical bonding of two or more polymers). From the viewpoint of achieving multiple properties, particulate polymers are particularly preferred to be particles composed of multiple polymers, more preferably core-shell structure particles having a core and a shell covering at least a portion of the outer surface of the core; particles with a side-by-side structure of two or more polymers arranged side-by-side; particles with a structure in which a portion of the polymer in the center is exposed to the outer shell; particles with a structure in which other types of polymer particles are embedded in the surface of spherical polymer particles to form an integrated structure, and even more preferably core-shell structure particles. By using particulate polymers with core-shell structures as particulate polymers, both high-performance adhesion and dispersion stability can be achieved, making them particularly preferred.

[0070] The following is an example of a particulate polymer with a core-shell structure.

[0071] (Particulate polymers with a core-shell structure)

[0072] The particulate polymer with a core-shell structure has a core and a shell covering the outer surface of the core. By using the particulate polymer with the core-shell structure, inkjet ejection characteristics can be improved.

[0073] Here, the shell may cover the entire outer surface of the core, or it may partially cover the outer surface of the core. Even if the outer surface of the core sometimes appears to be completely covered by the shell, if a hole is formed connecting the inside and outside of the shell, then the shell is a shell that partially covers the outer surface of the core.

[0074] Particulate polymers may have any structural elements other than the core and shell described above, provided that the desired effect is not significantly impaired. Specifically, for example, a particulate polymer may also have a portion inside the core formed of a polymer different from the core. As a specific example, seed particles used in the production of particulate polymers using seed polymerization may remain inside the core. However, from the viewpoint of significantly achieving the desired effect, particulate polymers preferably have only a core and a shell.

[0075] (Nuclear Department)

[0076] The glass transition temperature of the polymer in the core of the particulate polymer is preferably -50°C or higher, more preferably -45°C or higher, more preferably 60°C or lower, more preferably 35°C or lower, even more preferably 0°C or lower, and even more preferably -15°C or lower.

[0077] If the glass transition temperature of the polymer in the core is above the aforementioned lower limit, inkjet ejection characteristics can be improved. On the other hand, if the glass transition temperature of the polymer in the core is below the aforementioned upper limit, the polymer in the core exhibits good adhesion, and an adhesive layer that more firmly bonds the battery components together can be formed even under pressure at room temperature. Furthermore, if the glass transition temperature of the polymer in the core is below the aforementioned upper limit, the shedding of components contained in the adhesive layer (so-called powder shedding) can be sufficiently suppressed.

[0078] The glass transition temperature of the polymer in the core can be adjusted, for example, by changing the type and proportion of monomers used in the preparation of the polymer in the core.

[0079] Examples of monomers used to prepare the polymer core include: vinyl chloride monomers such as vinyl chloride and vinylidene chloride; vinyl acetate monomers such as vinyl acetate; aromatic vinyl monomers such as styrene, α-methylstyrene, styrene sulfonic acid, butoxystyrene, and vinylnaphthalene; vinylamine monomers such as vinylamine; vinylamide monomers such as N-vinylformamide and N-vinylacetamide; non-fluorinated (meth)acrylate monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; (meth)acrylamide monomers such as acrylamide and methacrylamide; (meth)acrylonitrile monomers such as acrylonitrile and methacrylonitrile; fluorinated (meth)acrylate monomers such as 2-(perfluorohexyl)ethyl methacrylate and 2-(perfluorobutyl)ethyl acrylate; maleimide; and maleimide derivatives such as phenylmaleimide. These can be used individually or in combination of two or more in any ratio.

[0080] In this invention, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid, and (meth)acrylonitrile refers to acrylonitrile and / or methacrylonitrile.

[0081] Among these monomers, from the viewpoint of making the battery components adhere more firmly to each other via the adhesive layer, it is preferable to use at least a (meth)acrylate monomer as the monomer used to prepare the polymer of the core, more preferably using a combination of (meth)acrylate monomer and aromatic vinyl monomer, or a combination of (meth)acrylate monomer and (meth)acrylonitrile monomer. That is, the polymer of the core preferably contains at least a (meth)acrylate monomer unit, more preferably a combination of (meth)acrylate monomer unit and aromatic vinyl monomer unit, or a combination of (meth)acrylate monomer unit and (meth)acrylonitrile monomer unit.

[0082] In this invention, "containing monomer units" means "containing repeating units from the monomer in a polymer obtained by using the monomer".

[0083] Furthermore, in this invention, "(meth)acrylate monomer" refers to a monofunctional (meth)acrylate monomer having only one polymerization reactive group.

[0084] From the viewpoint of making the battery components more firmly bonded to each other through the adhesive layer, all repeating units (all monomer units) in the particulate polymer are taken as 100% by mass, and the proportion of (meth)acrylate monomer units in the polymer of the core is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 98% by mass or less, and more preferably 96% by mass or less.

[0085] When the polymer in the core contains (meth)acrylate monomer units and aromatic vinyl monomer units, from the viewpoint of making the battery components more firmly bonded to each other via the adhesive layer, taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of (meth)acrylate monomer units in the polymer in the core is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. Furthermore, taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of aromatic vinyl monomer units in the polymer in the core is preferably 15% by mass or more, more preferably 20% by mass or more, particularly preferably 25% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

[0086] When the polymer in the core contains (meth)acrylate monomer units and (meth)acrylonitrile monomer units, from the viewpoint of making the battery components more firmly bonded to each other via the adhesive layer, taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of (meth)acrylate monomer units in the polymer in the core is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 85% by mass or more, preferably 98% by mass or less, more preferably 96% by mass or less. Furthermore, taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of (meth)acrylonitrile monomer units in the polymer in the core is preferably 1% by mass or more, more preferably 1.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less.

[0087] The polymer in the core can contain monomer units with acidic groups. Examples of monomers with acidic groups include monomers with carboxylic acid groups, monomers with sulfonic acid groups, and monomers with phosphate groups.

[0088] Examples of monomers containing a carboxylic acid group include monocarboxylic acids and dicarboxylic acids. Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid. Examples of dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.

[0089] In addition, examples of monomers having sulfonic acid groups include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth)allyl sulfonic acid, ethyl (meth)acrylic acid-2-sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid.

[0090] Furthermore, examples of monomers with phosphate groups include 2-(meth)acryloyloxyethyl phosphate, methyl-2-(meth)acryloyloxyethyl phosphate, and ethyl-(meth)acryloyloxyethyl phosphate.

[0091] In this invention, (methyl)allyl refers to allyl and / or methylallyl, and (meth)acryloyl refers to acryloyl and / or methacryloyl.

[0092] Among these, monomers containing acidic groups are preferred, especially those with carboxylic acid groups, particularly monocarboxylic acids, and more preferably (meth)acrylic acid.

[0093] Furthermore, monomers containing acidic groups can be used alone or in combination of two or more in any ratio.

[0094] Taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of acid-containing monomer units in the core polymer is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 15% by mass or less, and more preferably 10% by mass or less. By keeping the proportion of acid-containing monomer units within the above range, the dispersibility of the core polymer can be improved during the preparation of the particulate polymer, and a shell portion partially covering the outer surface of the core polymer can be easily formed.

[0095] The polymer in the core preferably includes crosslinking monomer units in addition to the monomer units mentioned above. Crosslinking monomers are monomers that can form crosslinked structures during or after polymerization by heating or irradiation with energy lines.

[0096] Examples of crosslinking monomers include polyfunctional monomers having two or more polymerization-reactive groups. Examples of such polyfunctional monomers include: divinylbenzene, 1,3-butadiene, isoprene, allyl methacrylate, etc.; di(meth)acrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,3-butanediol diacrylate, etc.; tri(meth)acrylate monomers such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, etc.; olefinically unsaturated monomers containing epoxy groups such as allyl glycidyl ether, glycidyl methacrylate, etc.; γ-methacryloyloxypropyltrimethoxysilane, N-hydroxymethylacrylamide, etc. Among these, di(meth)acrylate monomers are more preferred. Furthermore, these can be used alone or in combination of two or more in any ratio.

[0097] Taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of crosslinked monomer units in the polymer of the core is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By keeping the proportion of crosslinked monomer units within the above range, the battery components can be more firmly bonded to each other via the adhesive layer.

[0098] (Shell)

[0099] The glass transition temperature of the polymer in the shell of the granular polymer is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 80°C or higher, preferably 200°C or lower, and more preferably 120°C or lower.

[0100] If the glass transition temperature of the polymer in the casing is above the lower limit mentioned above, the formation of agglomerates can be suppressed, and the inkjet ejection characteristics can be further improved. On the other hand, if the glass transition temperature of the polymer in the casing is below the upper limit mentioned above, the particulate polymer softens moderately, so that an adhesive layer that can more firmly bond the battery components together can be formed even under pressure at room temperature.

[0101] The glass transition temperature of the polymer in the shell can be adjusted, for example, by changing the type and proportion of monomers used in the preparation of the polymer in the shell.

[0102] Furthermore, from the viewpoint of maintaining the shape of the granular polymer after the battery components are bonded together and suppressing the increase of resistance, it is preferable that the glass transition temperature of the polymer in the shell is 25°C or more higher than that of the polymer in the core.

[0103] Examples of monomers used as monomers for preparing the shell of a polymer include those exemplified as monomers used to manufacture the core of a polymer. Furthermore, such monomers can be used alone or in combination of two or more in any ratio.

[0104] Among these monomers, from the viewpoint of more firmly bonding the battery components together via the adhesive layer, at least one of (meth)acrylate monomers, aromatic vinyl monomers, (meth)acrylonitrile monomer units, and monomers containing acidic groups is more preferred as the monomer used to prepare the polymer of the casing. That is, the polymer of the casing preferably contains at least one of (meth)acrylate monomer units, aromatic vinyl monomer units, (meth)acrylonitrile monomer units, and monomer units containing acidic groups.

[0105] Furthermore, from the viewpoint of further firmly bonding the battery components together via the adhesive layer, taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of (meth)acrylate monomer units in the polymer of the shell is preferably 1% by mass or more, more preferably 1.5% by mass or more, preferably 10% by mass or less, and more preferably 6% by mass or less.

[0106] From the viewpoint of further firmly bonding the battery components together via the adhesive layer, all repeating units (all monomer units) in the particulate polymer are taken as 100% by mass, and the proportion of aromatic vinyl monomer units in the polymer of the shell is preferably 2% by mass or more, more preferably 3% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less.

[0107] Taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of (meth)acrylonitrile monomer units in the polymer of the shell is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

[0108] Taking all repeating units (all monomer units) in the particulate polymer as 100% by mass, the proportion of acidic monomers in the polymer of the shell is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less.

[0109] (The mass percentage of the shell in the total mass of the core and shell)

[0110] In the particulate polymer, the mass percentage of the shell portion in the total mass of the core and shell portion is preferably 2% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0111] If the mass ratio of the housing portion is above the lower limit mentioned above, the inkjet ejection characteristics can be further improved. On the other hand, if the mass ratio of the housing portion is below the upper limit mentioned above, an adhesive layer that can more firmly bond the battery components together can be formed even under room temperature and pressure.

[0112] Here, the mass ratio of the shell portion to the total mass of the core and shell portions is determined based on the ratio of the thickness of the core portion to the shell portion and the specific gravity of the particulate polymer, as described later.

[0113] (Preparation method of particulate polymers with core-shell structure)

[0114] Particulate polymers can be prepared by, for example, polymerizing monomers of a core polymer and monomers of a shell polymer in stages, changing the ratio of these monomers over time. Specifically, particulate polymers can be prepared by continuous multi-stage emulsion polymerization and multi-stage suspension polymerization, in which a polymer in a later stage is sequentially coated onto a polymer in a previous stage.

[0115] (Particulate polymers other than those with a core-shell structure: auxiliary particulate polymers)

[0116] In addition to the core-shell structured particulate polymer described above, the binder composition of the present invention may also contain other particulate polymers, or may contain other particulate polymers instead of the core-shell structured particulate polymers described above. For example, by containing both the core-shell structured particulate polymer and other particulate polymers, it is possible to prevent the components contained in the layer formed by the binder composition from detaching from the layer in a secondary battery. This effect is particularly advantageous when the binder composition forms an adhesive layer in a secondary battery. Hereinafter, for ease of distinction, such non-core-shell particulate polymers used as an auxiliary in addition to the core-shell structured particulate polymer will be referred to as "auxiliary particulate polymers".

[0117] The auxiliary particulate polymer can be particles formed by granulating only one type of polymer, or particles formed by granulating a mixture of multiple polymers. The glass transition temperature of the auxiliary particulate polymer is preferably below 25°C, more preferably below 10°C, and even more preferably below 0°C.

[0118] If the glass transition temperature of the polymer is below 25°C, the shedding of the components contained in the adhesive layer can be effectively suppressed, and the adhesion between the battery components of the secondary battery can be improved.

[0119] Examples of monomers used to prepare auxiliary particulate polymers include monomers that are the same monomers exemplified as monomers used to manufacture the core of the aforementioned particulate polymers. For example, monomers used to prepare polymers as auxiliary particulate polymers include (meth)acrylate monomers, (meth)acrylonitrile monomers, aromatic vinyl monomer units, monomers containing acid groups, (meth)acrylamide monomers, and crosslinking monomers.

[0120] Furthermore, as monomers for preparing polymers as auxiliary particulate polymers, (meth)acrylate monomers with polar groups, such as (meth)acrylate-2-hydroxyethyl acrylate and (meth)acrylate-2-hydroxypropyl acrylate, can also be used.

[0121] In addition, one of the above monomers can be used alone, or two or more can be used in any ratio.

[0122] In one embodiment, the monomers used to prepare the polymer as an auxiliary particulate polymer can be a combination of (meth)acrylate monomers, (meth)acrylonitrile monomers, acid-containing monomers, (meth)acrylamide monomers, and crosslinking monomers, or a combination of aromatic vinyl monomers, acid-containing monomers, (meth)acrylate monomers with polar groups, and crosslinking monomers. That is, the polymer as an auxiliary particulate polymer can contain (meth)acrylate monomer units, (meth)acrylonitrile monomer units, acid-containing monomer units, (meth)acrylamide monomer units, and crosslinking monomer units, or it can contain aromatic vinyl monomer units, acid-containing monomer units, (meth)acrylate monomer units with polar groups, and crosslinking monomer units.

[0123] The proportion of (meth)acrylate monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, 40% by mass or more, 50% by mass or more, 60% by mass or more, for example, 90% by mass or less, or 85% by mass or less.

[0124] The proportion of (meth)acrylonitrile monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, more than 1% by mass, more than 5% by mass, more than 10% by mass, for example, less than 20% by mass, or less than 15% by mass.

[0125] The proportion of acid-containing monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, for example, 10% by mass or less, 7% by mass or less, or 5% by mass or less.

[0126] The proportion of (meth)acrylamide monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, more than 0.1% by mass, more than 0.5% by mass, more than 1% by mass, for example, less than 5% by mass, less than 4% by mass, or less than 2% by mass.

[0127] The proportion of aromatic vinyl monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, more than 20% by mass, more than 40% by mass, more than 55% by mass, for example, less than 80% by mass, less than 70% by mass, or less than 65% by mass.

[0128] The proportion of (meth)acrylate monomer units with polar groups in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, 0.1% by mass or more, 0.5% by mass or more, for example, 3% by mass or less, or 1.5% by mass or less.

[0129] The proportion of crosslinking monomer units in the polymer used as an auxiliary particulate polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, more than 1% by mass, more than 2% by mass, more than 3% by mass, for example, less than 50% by mass, less than 40% by mass, or less than 35% by mass.

[0130] When the polymer used as an auxiliary particulate polymer contains crosslinking monomer units and (meth)acrylonitrile monomer units, the proportion of crosslinking monomer units in the polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, more than 1% by mass, more than 2% by mass, more than 3% by mass, for example, less than 6% by mass, less than 5% by mass, or less than 4% by mass.

[0131] When the polymer used as an auxiliary particulate polymer contains crosslinking monomer units (methyl) and aromatic vinyl monomer units, the proportion of crosslinking monomer units in the polymer is not particularly limited. All repeating units (all monomer units) contained in the polymer are taken as 100% by mass, for example, 10% by mass or more, 20% by mass or more, or 30% by mass or more, for example, 50% by mass or less, 40% by mass or less, or 35% by mass or less.

[0132] The volume average particle size of the auxiliary particulate polymer is preferably 50 nm or more, more preferably 100 nm or more, even more preferably 200 nm or more, preferably 600 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less. If the volume average particle size of the auxiliary particulate polymer is within the above-mentioned range, the battery components can be more firmly bonded together by the adhesive material.

[0133] The amount of auxiliary particulate polymer is not particularly limited, but it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, relative to 100 parts by mass of the core-shell structured particulate polymer. If the amount of auxiliary particulate polymer is within the above range, it is possible to sufficiently prevent the detachment of the components contained in the adhesive layer and improve the cycle characteristics of the secondary battery.

[0134] The amount of auxiliary particulate polymer in the binder composition is not particularly limited, but from the viewpoint of suppressing agglomeration, a lower amount is preferred. Specifically, the amount of auxiliary particulate polymer in 100% by mass of the binder composition is preferably 5% by mass or less. When the binder composition contains auxiliary particulate polymer, the lower limit of its amount can be, for example, 0.2% by mass or more.

[0135] The binder composition may not contain auxiliary particulate polymers. Without auxiliary particulate polymers, the formation of aggregates is effectively suppressed. Furthermore, the increase in the internal resistance of the resulting secondary battery can be suppressed, further improving cycle characteristics.

[0136] The polymer used as an auxiliary particulate polymer is not particularly limited, and can be prepared, for example, by polymerizing a monomer composition containing the aforementioned monomers in an aqueous solvent such as water. Here, the proportion of each monomer in the monomer composition is generally the same as the proportion of each monomer unit in the polymer. Furthermore, there are no particular limitations on the polymerization method and polymerization reaction, and known polymerization methods and reactions can be used.

[0137] (Dispersion medium)

[0138] The binder composition preferably contains water as a dispersion medium, but may also contain dispersion media other than water. Examples of dispersion media other than water include: cyclic aliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, γ-butyrolactone, and ε-caprolactone; nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran; and organic solvents such as alcohols such as methanol, ethanol, and isopropanol.

[0139] (Desiccant)

[0140] By containing an anti-drying agent, the adhesive composition can suppress drying of the adhesive composition during storage using adhesive packaging, and can more effectively suppress the formation of agglomerate particles.

[0141] Low molecular weight polyol compounds can be used as anti-drying agents. Low molecular weight polyol compounds are those with a molecular weight less than 150 and containing two or more hydroxyl groups (-OH) per molecule. By including low molecular weight polyol compounds, the binder composition not only inhibits drying of the binder composition during storage but also improves the ejection characteristics when the binder composition is ejected from the inkjet head.

[0142] Examples of low molecular weight polyol compounds include propylene glycol, ethylene glycol, glycerol, 1,3-propanediol, and 1,4-butanediol. Glycerol is preferred among these. These compounds can be used alone or in combination of two or more in any ratio.

[0143] The content of low molecular weight polyol compound relative to 100 parts by weight of particulate polymer is preferably 20 parts by weight or more, more preferably 40 parts by weight or more, even more preferably 50 parts by weight or more, even more preferably 55 parts by weight or more, preferably 400 parts by weight or less, more preferably 300 parts by weight or less, even more preferably 250 parts by weight or less, and even more preferably 200 parts by weight or less.

[0144] If the content of the aforementioned low molecular weight polyol compound is above the lower limit, the generation of agglomerated particles can be reduced, and the inkjet ejection characteristics can be further improved. On the other hand, if the content of the aforementioned low molecular weight polyol compound is below the upper limit, the excessive increase in viscosity of the binder composition can be suppressed, resulting in further improvement in inkjet ejection characteristics.

[0145] The content of the low molecular weight polyol compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 29 parts by mass or less, relative to 100 parts by mass of water as the dispersion medium.

[0146] If the content of the aforementioned low molecular weight polyol compound is above the lower limit, the generation of agglomerated particles can be reduced, and the inkjet ejection characteristics can be further improved. On the other hand, if the content of the aforementioned low molecular weight polyol compound is below the upper limit, the excessive increase in viscosity of the binder composition can be suppressed, resulting in further improvement in inkjet ejection characteristics.

[0147] (Other components of the adhesive composition)

[0148] In addition to the components described above, the binder composition may contain any other components. For example, it may contain a dispersant (water-soluble polymer) for inhibiting aggregation and a dispersion stabilizer. Examples of dispersants include ammonium acrylate polymers (e.g., ARON (registered trademark) A-6114 manufactured by Toa Synthetic Co., Ltd.).

[0149] (Properties of the adhesive composition, etc.)

[0150] The binder composition preferably undergoes a stage before being filled into a container and forming the binder packaging of the present invention, during which particulate components such as coarse particles and agglomerate particles are filtered to reduce their concentration. Specifically, the concentration of particulate components is preferably 1000 ppm or less, more preferably 800 ppm or less, and even more preferably 500 ppm or less.

[0151] Furthermore, by employing the above-described structure, the adhesive packaging of the present invention can maintain a low concentration of particulate components in the adhesive composition even after long-term storage. Specifically, the concentration of particulate components in the adhesive composition contained in the adhesive packaging stored at an environment of 5°C or higher and 40°C or lower for 6 months is preferably 1000 ppm or lower, more preferably 800 ppm or lower, and even more preferably 500 ppm or lower.

[0152] From the viewpoint of ease of operation, the surface tension of the binder composition is preferably 20 to 60 mN / m.

[0153] (Modified Example)

[0154] The adhesive packaging of the present invention is not limited to the above examples, and modifications to the above examples are also possible.

[0155] For example, in Figure 1 The example shown is a container 100 with a generally circular storage section 110, but the shape of the storage section is not limited to this and may also be square.

[0156] In addition, Figure 1 and Figure 2In the example, the adhesive composition is drawn from upstream of connector 150 by a pump, while gas is introduced from the opening 159L of connector to the top side opening 129H of liquid delivery adapter 120, thereby exporting the adhesive composition. However, the exporting operation is not limited to this. For example, container 100 may have an opening communicating with the external environment of the container via a filter instead of the air supply port 129 communicating with the opening of connector 150, and external air may be introduced from there. Alternatively, the exporting of the adhesive composition may also be carried out by pressurizing and deforming the receiving part 110 from the outside, thereby creating a positive pressure in the internal space 101 of the container, thereby pressurizing the adhesive composition. Furthermore, in Figure 1 and Figure 2 In the example, the through hole 121 in the liquid delivery adapter 120 is a hole of a simple shape, but the shape of the through hole is not limited to this, and it can also be a through hole with, for example, a pressure reducing valve that facilitates extraction by a pump.

[0157] Example

[0158] The following embodiments illustrate the present invention in detail. However, the present invention is not limited to the following embodiments, and can be implemented in any way without departing from the scope of the claims and their equivalents.

[0159] In the following descriptions, unless otherwise stated, "%" and "parts" refer to quantities based on weight. Furthermore, unless otherwise stated, the operations described below are performed under normal temperature and pressure conditions.

[0160] [Evaluation Method]

[0161] (Glass transition temperature)

[0162] A particulate polymer aqueous dispersion was dried at 130°C for 1 hour to prepare the test sample. 10 mg of the test sample was weighed into an aluminum dish, and the measurement was performed using a differential scanning calorimetry (DSC) apparatus (Seiko Electronics Nanotechnology Co., Ltd., "EXSTARDSC6220") within the measurement temperature range of -100°C to 200°C, at a heating rate of 10°C / min, under the conditions specified in JIS Z8703, to obtain the differential scanning calorimetry (DSC) curve. An empty aluminum dish was used as a reference during the measurement. During this heating process, the intersection of the baseline of the DSC curve before the endothermic peak appears (when the differential signal (DDSC) is 0.05 mW / min / mg or higher) and the tangent line of the DSC curve at the first inflection point after the endothermic peak was determined as the glass transition temperature (°C).

[0163] (Volume average particle size)

[0164] The volume-average particle size of the particulate polymer was determined using laser diffraction. Specifically, water was added to an aqueous dispersion containing the prepared particulate polymer, and the solids concentration was adjusted to 0.1% by mass as a sample. The particle size distribution (volume basis) was determined using a laser diffraction particle size distribution measuring device (Beckman Coulter, product name "LS-13 320"). From the particle size distribution, the particle size that accounts for 50% of the cumulative volume from the smallest particle size side was determined as the volume-average particle size D50 (nm).

[0165] (Contact Angle)

[0166] Prepare a component identical to the housing 110 used in the examples and comparative examples, and cut it to create a flat sample. With the surface corresponding to the inner wall 102 facing upwards, add water and the adhesive composition used in the examples and comparative examples to form a droplet. Using a contact angle meter (manufactured by Kyowa Interface Chemicals Co., Ltd., product name "DMs-400"), perform image analysis based on the tangent method on the image of the droplet obtained from the horizontal direction to determine the contact angle.

[0167] (Concentration of particulate components)

[0168] Weigh a cleaned nylon mesh filter with a pore size of 5 μm. Filter 1 kg of the binder composition to be tested using this mesh filter. After washing the collected material with deionized water, dry it at 80°C for 3 hours. After drying, weigh the mesh filter containing the collected material.

[0169] Calculate the difference between the weighing value after collection and the weighing value before collection, and use this value as the amount of particulate component to calculate the concentration in the analyte. Evaluate the concentration calculated using the following benchmarks.

[0170] A: Less than 500 ppm.

[0171] B: Above 500ppm and below 800ppm.

[0172] C: Above 800ppm and less than 1000ppm.

[0173] D: 1000μm or more and less than 3000μm.

[0174] E: Above 3000ppm.

[0175] (Inkjet ejection characteristics)

[0176] In each embodiment and comparative example, the binder composition extracted from the container and transferred to the coating machine is supplied to the nozzle head of the ejection test kit for continuous ejection. As the ejection test kit and nozzle head, an ejection test kit (IJK-200S, manufactured by Microjet Corporation) equipped with a high-performance glass nozzle (IJHD-100) is used. The ejection conditions are a droplet volume of 100 pL and an ejection frequency of 500 kHz. The ejection characteristics are evaluated according to the following benchmarks.

[0177] A: It did not become unable to spray continuously for less than 12 hours after the start of continuous spraying.

[0178] B: During the period of more than 9 hours but less than 12 hours after the start of continuous spraying, it becomes unable to spray continuously.

[0179] C: During the period of more than 6 hours but less than 9 hours after the start of continuous spraying, it becomes unable to spray continuously.

[0180] D: During the period of more than 3 hours but less than 6 hours after the start of continuous spraying, it becomes unable to spray continuously.

[0181] E: It becomes unable to spray continuously for less than 3 hours after the start of continuous spraying.

[0182] (Dry bond strength)

[0183] Under the same conditions as in the embodiments and comparative examples, a binder composition was supplied to one surface of the pressed negative electrode raw material, and spacers were further overlapped thereon. The mixture was then pressed for 10 seconds at a temperature of 25°C and a pressure of 1 MPa. This yielded a laminate containing the negative electrode raw material, the binder composition, and the spacers. The laminate was cut to obtain numerous elongated rectangular test pieces with dimensions of 500 mm × 200 mm.

[0184] Secure the transparent tape to a horizontal test stage with the adhesive side facing up. Adhere the test piece to the transparent tape with the negative side facing down. Use the transparent tape specified in JIS Z1522. Stretch and peel the spacer vertically upwards at a tensile speed of 50 mm / min from one end along its length, and measure the stress during peeling.

[0185] A total of six measurements were performed, and the average stress was calculated. This average value was taken as the peel strength. The peel strength was evaluated according to the following criteria. A higher peel strength indicates a stronger dry adhesion between the electrode and the spacer due to the drying of the coating solution.

[0186] A: Peel strength is above 5.0 N / m

[0187] B: Peel strength is 4.0 N / m or higher and less than 5.0 N / m

[0188] C: Peel strength is ≥3.0 N / m and <4.0 N / m

[0189] D: Peel strength is above 1.0 N / m and less than 3.0 N / m

[0190] E: Peel strength less than 1.0 N / m

[0191] (Cyclic Characteristics)

[0192] The lithium-ion secondary batteries fabricated in the examples and comparative examples were charged to 4.3V using a constant current and constant voltage (CC CV) method at 25°C. The charged batteries were then discharged to 3.0V using a constant current method at 0.2C and 1C at -10°C, and their capacities were determined. The discharge capacity retention rate, expressed as the ratio of capacitance (=(Capacity at 1C / Capacity at 0.2C)×100(%)), was then calculated. These measurements were performed on five lithium-ion secondary batteries, and the average of the calculated discharge capacity retention rates was taken as the output characteristic.

[0193] Next, the lithium-ion secondary battery was clamped with a pressure fixture to a surface pressure of 1 MPa and subjected to a cycle test at 45°C. The cycle test conditions were 1C CC+CV charging (4.3V, 1 / 50C cutoff) and 1C CC discharging (3.0V cutoff), repeated for 500 charge-discharge cycles. Then, while maintaining the clamped state, the temperature was lowered to 25°C, and the output characteristics were measured in the same manner as above. The resistance retention rate (%) before and after cycling was calculated (=(average discharge capacity retention rate after cycle test / average discharge capacity retention rate before cycle test)×100), and evaluated according to the following criteria. The higher the resistance retention rate before and after cycling, the smaller the resistance rise during the cycle test, i.e., the better the cycle characteristics.

[0194] A: Resistance retention rate is over 80%.

[0195] B: Resistance retention rate is 70% or higher but less than 80%.

[0196] C: Resistance retention rate is 60% or higher but less than 70%.

[0197] D: Resistance retention rate is 40% or higher and less than 60%.

[0198] E: Resistance retention rate is less than 40%.

[0199] (Manufacturing Example 1)

[0200] 100 parts of ion-exchanged water and 0.1 parts of ammonium persulfate were supplied to a reactor equipped with a stirrer, the gas phase was replaced with nitrogen, and the temperature was raised to 80°C. Meanwhile, 40 parts of ion-exchanged water, 0.2 parts of sodium dodecylbenzenesulfonate as an emulsifier, and a core-forming monomer composition were mixed in another container to obtain a core-forming mixture.

[0201] As a core monomer composition, a composition consisting of 91.1 parts of n-butyl acrylate as a (meth)acrylate monomer, 1.9 parts of methacrylic acid as an acidic group monomer, 0.1 parts of ethylene glycol dimethacrylate as a crosslinking monomer, and 1.9 parts of acrylonitrile as a (meth)acrylonitrile monomer is used.

[0202] The core-forming mixture was continuously added to the reactor over 3 hours, and polymerization was carried out at 80°C. Polymerization continued until the polymerization conversion reached 95%, thereby obtaining an aqueous dispersion containing particulate polymers constituting the core. Then, the shell-forming monomer composition was continuously fed into the aqueous dispersion for 60 minutes, and polymerization continued.

[0203] As a monomer composition for the shell, a composition consisting of 4.75 parts of styrene as an aromatic vinyl monomer and 0.25 parts of methacrylic acid as an acidic group monomer is used.

[0204] The reaction was terminated by cooling when the polymerization conversion reached 98%, thereby preparing an aqueous dispersion containing particulate polymer 1. The volume average particle size and glass transition temperature of the obtained particulate polymer 1 were measured.

[0205] The cross-sectional structure of the particulate polymer 1 was observed using a transmission electron microscope (TEM), which confirmed that the particulate polymer 1 has a core-shell structure in which the shell part partially covers the outer surface of the core.

[0206] (Manufacturing Example 2)

[0207] Except for the changes described below, particulate polymer 2 was obtained by the same operation as in manufacturing example 1, and the volume average particle size and glass transition temperature were measured.

[0208] • As a monomer composition for the core, a composition consisting of 3 parts methacrylic acid, 48 parts 2-ethylhexyl acrylate, 43.9 parts styrene and 0.1 parts ethylene glycol dimethacrylate is used.

[0209] • As a monomer composition for the shell, a composition consisting of 4.7 parts of styrene, 0.05 parts of methacrylic acid and 0.25 parts of acrylonitrile is used.

[0210] The cross-sectional structure of the particulate polymer was observed using a transmission electron microscope (TEM), which confirmed that the particulate polymer 2 has a core-shell structure in which the shell part partially covers the outer surface of the core.

[0211] (Manufacturing Example 3)

[0212] In a reactor equipped with a stirrer, 90 parts of ion-exchanged water, 0.05 parts of sodium dodecylbenzenesulfonate (manufactured by Kao Chemical Co., Ltd., "NEOPLEX G-15") as an emulsifier, and 0.23 parts of ammonium persulfate were supplied, the gas phase was replaced with nitrogen, and the temperature was raised to 70°C.

[0213] On the other hand, in another container, 50 parts of deionized water, 0.1 parts of sodium dodecylbenzenesulfonate as an emulsifier, 2.3 parts of methacrylic acid as an acidic monomer, 12.5 parts of acrylonitrile as a (meth)acrylonitrile monomer, 79.9 parts of n-butyl acrylate as a (meth)acrylate monomer, 3.8 parts of N-hydroxymethylacrylamide as a crosslinking monomer, and 1.5 parts of acrylamide (AAm) as a (meth)acrylamide monomer were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor described above over 4 hours for polymerization. During the addition process, the reaction was carried out at 80°C. After the addition was completed, the mixture was further stirred at 80°C for 3 hours to terminate the reaction, producing an aqueous dispersion containing particulate polymer 3 without a core-shell structure.

[0214] The volume average particle size and glass transition temperature of the obtained particulate polymer 3 were measured.

[0215] Table 1 shows a summary of manufacturing examples 1-3 and the evaluation results. The abbreviations in Table 1 have the following meanings.

[0216] BA: Butyl acrylate percentage (%)

[0217] MAA: Methacrylic acid percentage (%)

[0218] AN: Acrylonitrile percentage (%)

[0219] 2EHA: Proportion of 2-ethylhexyl acrylate (%)

[0220] St: Styrene percentage (%)

[0221] NMA: N-hydroxymethylacrylamide ratio (%)

[0222] AAm: Acrylamide percentage (%)

[0223] EDMA: Ethylene glycol dimethacrylate ratio (%)

[0224] Shell proportion: The percentage of the total mass of the core and shell (%).

[0225] [Table 1]

[0226] Table 1

[0227]

[0228] (Example 1)

[0229] (1-1. Adhesive composition)

[0230] A mixture was prepared by mixing 10 parts (based on solids) of an aqueous dispersion of particulate polymer 1 obtained in Manufacturing Example 1, 1 part (based on solids) of an aqueous dispersion of particulate polymer 3 obtained in Manufacturing Example 3, 10 parts of propylene glycol as an anti-drying agent, and 0.1 parts (based on solids) of an ammonium acrylate polymer (manufactured by Toa Synthetic Co., Ltd., ARON (registered trademark) A-6114) as a dispersant (water-soluble polymer). Ion-exchanged water was further added to adjust the concentration so that the solids concentration was 11.1% by mass, thus obtaining a mixture. The mixture was filtered through a mesh filter with a pore size of 5 μm to obtain a binder composition.

[0231] The concentration of the granular component in the obtained binder composition was determined and evaluated.

[0232] (1-2. Containers)

[0233] Prepare with Figure 1 The container with the structure schematically shown in the figure and having Figure 2 The connector 150 schematically shown is an inkjet coating machine (Konica, KM1024 (shear-mode type)). Container 100 has a 10-liter HDPE (high-density polyethylene) housing 110, an HDPE liquid delivery adapter 120, an HDPE liquid delivery tube 130, and a stopper 140. The liquid delivery adapter 120 is screwed into and engages with the opening 111 of the housing 110, and the liquid delivery tube 130 has a structure that engages with the hand-side opening 121L of the liquid delivery adapter 120. The stopper 140 has a structure that is detachably screwed into and engages near the top of the liquid delivery adapter 120. These structural elements form an airtight internal space 101 within container 100.

[0234] The contact angle θ between the inner wall surface 102 of container 100 and water is measured. W and the contact angle θ with the adhesive composition obtained in (1-1) B .

[0235] (1-3. Adhesive Packaging)

[0236] Remove the plug 140 from the container 100 obtained in (1-2), and clean the container 100 to make its interior clean. Fill the internal space 101 of the container 100 with 9 liters of the freshly filtered adhesive composition obtained in (1-1), screw the plug 140 back on, and seal the container 100 to obtain the adhesive package.

[0237] The resulting adhesive packaging was stored indoors for 6 months. The room temperature during storage was in the range of 5–40°C.

[0238] After the storage period ends, the plug 140 is removed from container 100, a portion of the binder composition is extracted, and the concentration of the granular component is determined and evaluated.

[0239] The liquid delivery adapter 120 of container 100 is connected to the connector 150 of the coating machine. The adhesive composition is drawn from container 100 and delivered to the coating machine via the liquid delivery pump of the coating machine. During the drawing process, coarse particles with a content of 2000 particles / m³ are simultaneously introduced into the container through the opening 159L of connector 150. 3 Clean air to the left and right.

[0240] The binder composition that has reached the coating machine is extracted, and the concentration of the granular component is determined and evaluated.

[0241] (1-4. Production of negative electrode raw materials)

[0242] In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene, 3.5 parts of itaconic acid, 63.5 parts of styrene, 0.4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added. After thorough stirring, the mixture was heated to 50°C to initiate polymerization. The reaction was terminated by cooling when the polymerization conversion reached 96%, yielding a mixture containing a binder material for the negative electrode composite layer (SBR). A 5% sodium hydroxide aqueous solution was added to the mixture to adjust the pH to 8, followed by heated vacuum distillation to remove unreacted monomers. The mixture was then cooled to below 30°C to obtain an aqueous dispersion containing the desired binder material for the negative electrode composite layer.

[0243] Next, 100 parts of artificial graphite (volume average particle size: 15.6 μm) as the negative electrode active material, 1 part of sodium carboxymethyl cellulose (manufactured by Nippon Paper Corporation, product name "MAC350HC") as a viscosity modifier (based on the solids content), and deionized water were mixed to adjust the solids content concentration to 68%, and then mixed for 60 minutes at 25°C. The solids content concentration was then adjusted to 62% using deionized water, and mixed for 15 minutes at 25°C. To the resulting mixture, 1.5 parts of the above-mentioned aqueous dispersion containing the binder material for the negative electrode composite layer (based on the solids content) and deionized water were added to adjust the final solids content concentration to 52%, and the mixture was further mixed for 10 minutes. The mixture was then degassed under reduced pressure to obtain a non-aqueous secondary battery negative electrode slurry composition with good flowability.

[0244] The obtained non-aqueous secondary battery negative electrode slurry composition was applied to both sides of a 20 μm thick strip of copper foil (serving as a current collector) using a corner-shaped coating machine, with a dried film thickness of approximately 150 μm. The foil was then dried by conveying it at 0.5 m / min in an oven at 60°C for 2 minutes. Next, it was heat-treated at 120°C for 2 minutes to obtain the negative electrode raw material before pressing. This raw material was then calendered using a roll press to obtain a pressed negative electrode raw material with a negative electrode composite layer thickness of 80 μm.

[0245] (1-5. Production of cathode raw materials)

[0246] 100 parts of LiCoO2 with a volume average particle size of 12 μm as the positive electrode active material, 2 parts of acetylene black (manufactured by Denka Co., Ltd., product name "HS-100") as the conductive material, 2 parts of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., product name "#7208") as the binder (based on solid content), and N-methylpyrrolidone as the solvent were mixed to achieve a total solid content concentration of 70%. These were then mixed using a planetary mixer to obtain a slurry composition for the positive electrode of a non-aqueous secondary battery.

[0247] The obtained non-aqueous secondary battery cathode slurry composition was coated onto both sides of a 20 μm thick strip of aluminum foil (serving as a current collector) using a corner-shaped coating machine, with a dried film thickness of approximately 150 μm. The foil was then dried by conveying it at 0.5 m / min in an oven at 60°C for 2 minutes. Finally, it was heat-treated at 120°C for 2 minutes to obtain the cathode raw material.

[0248] The obtained cathode raw material is then calendered using a roller press to obtain a pressed cathode raw material with a cathode composite material layer. The pressed cathode raw material is then further cut into rectangular shapes.

[0249] (1-6. Spacer Raw Materials)

[0250] Prepare the raw material for the long strip-shaped spacer made of polyethylene (PE) (product name: Asahi Kasei Corporation "ND412").

[0251] (1-7. Laminated structures for non-aqueous secondary batteries)

[0252] The pressed negative electrode raw material obtained in (1-4) is transported at a speed of 10 m / min, and an adhesive composition is supplied to one side surface of the negative electrode raw material, on which the spacer raw material (1-6), which serves as the first spacer raw material, is further overlapped and bonded using a pressing roller. The adhesive composition is supplied by ejecting the adhesive composition drawn from the container in (1-3) into the coating machine from the inkjet head of the coating machine.

[0253] Next, on the other side of the negative electrode raw material, an adhesive composition is supplied from another coating machine in the same manner as above, and another piece (1-6) of spacer raw material is further overlapped thereon as a second spacer raw material. The two pieces are then bonded together with a pressing roller to obtain a laminate (a) having a layer structure of (first spacer raw material) / (layer of adhesive composition) / (negative electrode raw material) / (layer of adhesive composition) / (second spacer raw material).

[0254] The adhesive composition is supplied to the surface of the first spacer raw material of the laminate (a) in the same manner as described above from another coating machine, and a rectangular positive electrode raw material is further overlapped thereon and bonded together with a pressing roller to obtain a laminate (b) having a layer structure of (rectangular positive electrode) / (layer of adhesive composition) / (first spacer raw material) / (layer of adhesive composition) / (negative electrode raw material) / (layer of adhesive composition) / (second spacer raw material).

[0255] Next, the adhesive composition is supplied from another coating machine to the positive electrode side of the laminate (b) in the same manner as described above, and the laminate (b) is cut. Thus, a rectangular laminate (c) is obtained having a layer structure of (layer of adhesive composition) / (rectangular positive electrode) / (layer of adhesive composition) / (first spacer) / (layer of adhesive composition) / (negative electrode) / (layer of adhesive composition) / (second spacer).

[0256] By shaping the slurry composition into appropriate forms, portions without an electrode composite layer (positive or negative) are provided at the ends of the current collectors of the positive and negative electrodes of the laminate (c), thus forming tabs of the desired size. The tabs of the positive and negative electrodes are arranged to extend from the same side of the rectangular laminate (c).

[0257] The bonding using the pressing rollers described above is performed at a temperature of 25°C and a pressure of 2 MPa. Furthermore, in the transport path of the respective newly pressed elongated laminates, the layers of the adhesive composition are dried at a drying temperature of 70°C and a drying time of 1 second by using heated rollers as transport rollers for transporting the laminates.

[0258] The adhesive compositions are supplied in a manner that forms a uniform dotted pattern. The dots are 100 μm in diameter and spaced 400 μm apart. The unit area mass (dry weight per unit area) of the adhesive composition is 0.2 g / m². 2 .

[0259] (1-8. Secondary batteries)

[0260] Five stacks (c) prepared in steps (1-7) were overlapped and pressed at 25°C and 2 MPa for 10 seconds to obtain stack (d). Stack (d) was packaged in an aluminum outer packaging, and an electrolyte (solvent: ethylene carbonate / diethyl carbonate / ethylene carbonate = 68.5 / 30 / 1.5 (volume ratio), electrolyte: 1M LiPF6) was injected into the outer packaging. The opening of the outer packaging was then sealed with heat at 150°C to produce a stacked lithium-ion secondary battery with a capacity of 800 mAh. The cycle characteristics of the obtained secondary battery were evaluated.

[0261] (Example 2)

[0262] In the preparation of the adhesive composition in (1-1), the particulate polymer 2 obtained in Manufacturing Example 2 was used instead of the particulate polymer 1. Otherwise, the same operation as in Example 1 was performed to obtain the adhesive package and evaluate it.

[0263] (Example 3)

[0264] In the preparation of the adhesive composition in (1-1), the proportion of particulate polymer 3 was changed from 10 parts to 5 parts, and the proportion of dispersant (water-soluble polymer) was changed from 0.1 parts to 0.05 parts, so that the total concentration of particulate polymers 1 and 3 was adjusted to 10.5%. Otherwise, the same operation as in Example 1 was performed to obtain the adhesive packaging and evaluate it.

[0265] (Example 4)

[0266] As the storage section 110 of container 100, a storage section made of polyethylene terephthalate of the same shape was used instead of the HDPE storage section used in Example 1. Otherwise, the same operation as in Example 1 was performed to obtain the adhesive package and evaluate it.

[0267] (Example 5)

[0268] In the preparation of the adhesive composition in (1-1), filtration was not performed, and the mixture of the components was used directly as the adhesive composition. Otherwise, the same operation as in Example 1 was performed to obtain the adhesive packaging and evaluate it.

[0269] (Example 6)

[0270] In the preparation of the adhesive composition in (1-1), no aqueous dispersion of the particulate polymer 3 was added, and the concentration was adjusted to a solid component concentration of 10.1% by mass. Otherwise, the same operation as in Example 1 was performed to obtain the adhesive package and evaluate it.

[0271] (Comparative Example 1)

[0272] Except for the changes described below, the same procedures as in Example 1 were performed to obtain the adhesive packaging and evaluate it.

[0273] • In the preparation of the binder composition in (1-1), the proportion of the dispersant (water-soluble polymer) is changed from 0.1 parts to 0.5 parts.

[0274] • As the storage section 110 of container 100, a storage section made of polyethylene terephthalate of the same shape is used instead of the storage section made of HDPE used in Example 1.

[0275] (Comparative Example 2)

[0276] Except for the changes described below, the same procedures as in Example 1 were performed to obtain the adhesive packaging and evaluate it.

[0277] • In (1-2), instead of using the liquid delivery adapter 120 and the liquid delivery tube 130, a container with a structure in which the opening 111 of the receiving part 110 is blocked by a plug is used.

[0278] • When dispensing the adhesive composition from the adhesive packaging in (1-3), remove the plug to open the opening, insert the tube from here, and use the dispensing pump of the coating machine to extract the adhesive composition using the tube.

[0279] A summary and results of the embodiments and comparative examples are shown in Table 2.

[0280] [Table 2]

[0281] Table 2

[0282]

[0283] Explanation of reference numerals in the attached figures

[0284] 100: Container

[0285] 101: Container internal space

[0286] 102: Inner wall surface

[0287] 110: Storage Department

[0288] 111: Opening

[0289] 120: Liquid delivery adapter

[0290] 121: Through hole

[0291] 121H: Top opening

[0292] 121L: Bottom side opening

[0293] 122: concave part

[0294] 123: Connector engagement part

[0295] 129: Air supply port

[0296] 129H: Top side opening

[0297] 129L: Bottom side opening

[0298] 130: Liquid delivery pipe

[0299] 131H: Top side end

[0300] 131L: Bottom side end

[0301] 140: Embolism

[0302] 150: Connector

[0303] 153: Connecting part

[0304] 151L: Open

[0305] 159L: Opening

[0306] 191: Screw joint

[0307] 192: Screw joint

Claims

1. An adhesive packaging having a container and an adhesive composition for a secondary battery housed within the internal space of the container, The container has a receiving section, a liquid delivery adapter, a liquid delivery tube, and a plug. The storage section has an opening at its top. The liquid delivery adapter is configured to engage with the opening of the receiving part. The bottom end of the delivery tube is close to the bottom of the internal space of the container, and the top end engages with the delivery adapter. The liquid delivery adapter and the liquid delivery pipe form a liquid guiding path connecting the opening at the bottom end of the liquid delivery pipe to the top side of the container. The plug body is detachably configured to engage with the liquid delivery adapter to seal the liquid delivery path. The contact angle θ between the adhesive composition and the inner wall surface of the container B The temperature is above 30°.

2. The adhesive packaging according to claim 1, wherein, The liquid delivery adapter has a locking part that can be connected to a connector for discharging the adhesive composition to the outside of the container.

3. The adhesive packaging according to claim 1 or 2, wherein, The adhesive composition comprises a particulate polymer with a glass transition temperature of 40°C or higher and 200°C or lower.

4. The adhesive packaging according to claim 1 or 2, wherein, The adhesive composition comprises a particulate polymer having a core-shell structure, the core-shell structure having a core and a shell covering the outer surface of the core, the glass transition temperature of the shell being above 40°C and below 200°C.

5. The adhesive packaging according to claim 4, wherein, The adhesive composition further comprises an auxiliary particulate polymer as a non-core-shell particulate polymer, wherein the auxiliary particulate polymer is present in a proportion of 5% by mass or less in 100% by mass of the adhesive composition.

6. The adhesive packaging according to claim 1 or 2, wherein, The adhesive composition comprises a particulate polymer consisting only of particulate polymers having a core-shell structure having a core and a shell covering the outer surface of the core.

7. The adhesive packaging according to claim 1 or 2, wherein, The adhesive composition comprises a particulate polymer, an anti-drying agent, and water, and the contact angle θ between the inner wall surface of the receiving portion and the water is [θ]. W It is above 80°.

8. The adhesive packaging according to claim 1 or 2, wherein, In an environment above 5°C and below 40°C, the concentration of particulate components with a spherical volume equivalent diameter of 5 μm or more in the adhesive composition contained in the adhesive packaging that has been stored for 6 months is below 1000 ppm.

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