Transdermal patch

Abstract

The present invention provides a transdermal patch suitable for releasing an active ingredient having a large molecular weight. A transdermal patch 10 according to the present invention is provided with a substrate 1 and a retaining layer 2 that retains an active ingredient. The active ingredient contains an organic compound C having a weight-average molecular weight of 1,000 or more. The retaining layer 2 contains a porous filler. In another aspect, the present invention provides a transdermal patch 11 provided with a substrate 1, a retaining layer 2 that retains an active ingredient, and an adhesive layer 3 in this order in the stacking direction, wherein: the active ingredient contains an organic compound C having a weight-average molecular weight of 1000 or more; and at least one layer selected from the group consisting of the retaining layer 2 and the adhesive layer 3 contains a porous filler.

Description

Patch

[0001] The present invention relates to a patch.

[0002] In fields such as agriculture, pesticides are used to prevent damage to plants caused by diseases and pests, and fertilizers are used to promote the growth of plants. As an example, agents such as pesticides and fertilizers are used by spraying them on the surface of plants in a liquid or powder state, or by mixing them in the soil in a solid state.

[0003] However, when spraying agents such as pesticides and fertilizers, the agents spread into the environment, and in some cases, there is a risk that workers may be exposed to the agents. In this method of use, the agents may be washed away by wind or rain. When the agent is mixed in the soil, the agent in the soil is not sufficiently absorbed by the plant, and most of it tends to remain in the soil.

[0004] On the other hand, according to the method of attaching a patch containing an agent to a plant, since the agent is directly taken up by the plant, there is a possibility of safely using the agent with the minimum required amount. As an example, Patent Document 1 discloses a weeding sheet containing a herbicide as an agent. This weeding sheet is a patch that can be attached to a plant and used.

[0005] Japanese Unexamined Patent Application Publication No. 2020-164515

[0006] According to the studies of the present inventors, when the molecular weight of the active ingredient contained in the patch is large, the active ingredient tends to be difficult to be released from the patch.

[0007] Therefore, an object of the present invention is to provide a patch suitable for releasing an active ingredient having a large molecular weight.

[0008] The present invention provides a patch including a base material and a holding layer that holds an active ingredient, the active ingredient including an organic compound having a weight average molecular weight of 1000 or more, and the holding layer including a porous filler.

[0009] Furthermore, the present invention provides a patch comprising a base material, a retaining layer for holding an active ingredient, and an adhesive layer in this order in the lamination direction, wherein the active ingredient comprises an organic compound having a weight-average molecular weight of 1000 or more, and at least one selected from the group consisting of the retaining layer and the adhesive layer contains a porous filler.

[0010] According to the present invention, it is possible to provide a patch suitable for releasing active ingredients with a large molecular weight.

[0011] This is a schematic cross-sectional view showing a patch according to one embodiment of the present invention. This is a schematic cross-sectional view showing a modified example of the patch.

[0012] A patch according to a first aspect of the present invention comprises a base material and a retaining layer for holding an active ingredient, wherein the active ingredient contains an organic compound having a weight-average molecular weight of 1000 or more, and the retaining layer contains a porous filler.

[0013] A second aspect of the present invention provides a patch comprising a base material, a retaining layer for holding an active ingredient, and an adhesive layer in this order in the lamination direction, wherein the active ingredient comprises an organic compound having a weight-average molecular weight of 1000 or more, and at least one selected from the group consisting of the retaining layer and the adhesive layer contains a porous filler.

[0014] In a third embodiment of the present invention, for example, in the patch according to the first or second embodiment, the organic compound includes a biopolymer.

[0015] In a fourth embodiment of the present invention, for example, in the patch according to the third embodiment, the biopolymer includes nucleic acid.

[0016] In a fifth embodiment of the present invention, for example, in the patch according to the fourth embodiment, the nucleic acid includes ribonucleic acid.

[0017] In a sixth aspect of the present invention, for example, in a patch according to any one of the first to fifth aspects, the average pore diameter of the porous filler is 200 nm or less.

[0018] In a seventh aspect of the present invention, for example, in a patch according to any one of the first to sixth aspects, the average pore diameter of the porous filler is 5 nm or more.

[0019] In the eighth aspect of the present invention, for example, in a patch according to any one of the first to seventh aspects, the median pore diameter of the porous filler is 10 nm or more.

[0020] In the ninth aspect of the present invention, for example, in a patch according to any one of the first to eighth aspects, the average particle size of the porous filler is 10 μm or less.

[0021] In a tenth aspect of the present invention, for example, in a patch according to any one of the first to ninth aspects, the porous filler includes at least one selected from the group consisting of carbon materials and silicon materials.

[0022] In the eleventh embodiment of the present invention, for example, in a patch according to any one of the first to tenth embodiments, the retaining layer is formed from an emulsion-based resin composition.

[0023] In a twelfth aspect of the present invention, for example, in the adhesive patch according to the eleventh aspect, the emulsion resin composition includes a (meth)acrylic polymer.

[0024] In a thirteenth aspect of the present invention, for example, in the adhesive patch according to the twelfth aspect, the (meth)acrylic polymer includes constituent units derived from a carboxyl group-containing monomer.

[0025] In a fourteenth aspect of the present invention, for example, in a patch according to the twelfth or thirteenth aspect, the (meth)acrylic polymer includes constituent units derived from silane monomers.

[0026] In the fifteenth aspect of the present invention, for example, in a patch according to any one of the eleventh to fourteenth aspects, the emulsion resin composition contains water as a dispersion medium.

[0027] In the sixteenth embodiment of the present invention, for example, a patch according to any one of the first to fifteenth embodiments is used on plants.

[0028] The details of the present invention will be described below, but the following description is not intended to limit the present invention to any particular embodiment.

[0029] <Dapet> Figure 1 is a schematic cross-sectional view of the adhesive patch 10 of this embodiment. The adhesive patch 10 comprises a base material 1 and a retaining layer 2. The retaining layer 2 is a layer that holds the active ingredient and may be in contact with the base material 1. In this embodiment, the active ingredient held by the retaining layer 2 contains an organic compound C with a weight-average molecular weight of 1000 or more. The retaining layer 2 further contains a porous filler.

[0030] In this embodiment, the retaining layer 2 can also function as an adhesive layer for attaching the patch 10 to an object (e.g., a plant). The patch 10 is configured such that when the retaining layer 2 is attached to the object, the active ingredient gradually moves from the retaining layer 2 to the object. The patch 10 functions as a sustained-release sheet that gradually releases the active ingredient to the object.

[0031] In conventional adhesive patches, when the molecular weight of the active ingredient is large, the active ingredient is not easily released from the patch even when it is applied to the target object, making it difficult to supply a sufficient amount of the active ingredient to the target object. In contrast, in the adhesive patch 10 of this embodiment, the retention layer 2 contains a porous filler, which makes it easier for the active ingredient to be released from the patch 10 to the target object, and even when the molecular weight of the active ingredient is large, it tends to be possible to supply a sufficient amount of the active ingredient to the target object.

[0032] (Substrate) The substrate 1 is a layered member that supports the retaining layer 2, and it is preferable that the active ingredients in the retaining layer 2 do not substantially pass through it. The physical properties and characteristics of the substrate 1 can be appropriately adjusted according to the active ingredients contained in the retaining layer 2 and the shape of the object. For example, if the active ingredients include a degradable organic compound such as ribonucleic acid (RNA), it is preferable that the substrate 1 has low UV and oxygen permeability. However, depending on the object (e.g., a plant), the oxygen permeability of the substrate 1 may be appropriately adjusted so as not to inhibit its respiration.

[0033] Furthermore, it is preferable that the base material 1 has antibacterial properties. A base material 1 with antibacterial properties can suppress the growth of bacteria and mold, which tends to suppress the decomposition of the active ingredient.

[0034] The base material 1 preferably has low water permeability. With a base material 1 that has low water permeability, it is possible to suppress the incorporation of water from the outside into the retaining layer 2 when the adhesive 10 is attached to the object. This tends to suppress excessive swelling of the retaining layer 2 and an excessive increase in the movement speed of the active ingredient from the retaining layer 2 to the object. However, in some cases, the water permeability of the base material 1 may be adjusted so that the movement speed of the active ingredient is appropriately controlled by measures such as spraying water from the outside.

[0035] The base material 1 is preferably flexible so that it can conform to the shape of the object. However, if the adhesive 10 may come into contact with an animal and cause damage, the flexibility of the base material 1 may be appropriately adjusted.

[0036] As the base material 1, a support made of any suitable material can be used, as long as it does not impair the effects of the present invention. Examples of base material 1 include resin films, paper, cloth, rubber sheets, foam sheets, metal foils, and composites thereof. Examples of resin films include polyolefin films such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer; polyester films such as polyethylene terephthalate (PET); vinyl chloride resin films; vinyl acetate resin films; polyimide resin films; polyamide resin films; fluororesin films; and cellophane. In this specification, a resin film is typically a non-porous resin sheet and is a concept distinct from, for example, nonwoven fabrics (i.e., does not include nonwoven fabrics). The resin film may be an unoriented film, a uniaxially oriented film, or a biaxially oriented film.

[0037] Examples of paper include Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, and topcoat paper. Examples of cloth include woven or nonwoven fabrics made from various fibrous materials individually or in blends. Examples of fibrous materials include cotton, rayon, Manila hemp, pulp, rayon, acetate fibers, polyester fibers, polyvinyl alcohol fibers, polyamide fibers, and polyolefin fibers. In this specification, nonwoven fabric may refer to nonwoven fabrics for adhesive sheets used primarily in the field of adhesive sheets, and may typically be nonwoven fabrics (sometimes referred to as "paper") produced using a general paper machine. Examples of rubber sheets include natural rubber sheets and butyl rubber sheets. Examples of foam sheets include foamed polyurethane sheets and foamed polychloroprene rubber sheets. Examples of metal foils include aluminum foil and copper foil. The surface of the substrate 1 on which the retaining layer 2 is provided may be subjected to surface treatments such as application of a primer, corona discharge treatment, or plasma treatment.

[0038] The base material 1 may further contain additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, and colorants.

[0039] The thickness of the substrate 1 is not particularly limited and may be, for example, 1 μm to 1000 μm, 5 μm to 500 μm, 7 μm to 300 μm, or even 10 μm to 100 μm.

[0040] (Retaining layer) In the patch 10, the retaining layer 2 has a surface exposed to the outside of the patch 10, and the patch 10 can be attached to the object via this surface. The retaining layer 2 is configured so that the active ingredient can move from the retaining layer 2 to the object when the patch 10 is attached to the object.

[0041] As described above, the holding layer 2 contains an active ingredient and a porous filler. The active ingredient is typically something that can be used as a drug. As described above, the active ingredient contains an organic compound C having a weight average molecular weight of 1000 or more. The weight average molecular weight of the organic compound C may be 3000 or more, 5000 or more, 8000 or more, 10000 or more, 15000 or more, 20000 or more, 25000 or more, 30000 or more, 50000 or more, 100000 or more, and even 500000 or more. The upper limit of the weight average molecular weight of the organic compound C is not particularly limited, and for example, it may be 5000000 or less, or 1000000 or less.

[0042] The organic compound C preferably contains a biopolymer. Examples of biopolymers include nucleic acids, peptides, proteins, etc., and it is preferable to contain a nucleic acid. The nucleic acid may be double-stranded or single-stranded. Examples of nucleic acids include ribonucleic acid (RNA) and deoxyribonucleic acid (DNA), and it is preferable to contain RNA. Specific examples of RNA include mRNA and siRNA. The number of bases of the nucleic acid is not particularly limited, and for example, it may be 20 or more, 100 or more, and even 1000 or more. The upper limit of the number of bases of the nucleic acid is, for example, 10000 or less, or 5000 or less. The active ingredient may be a virus or viroid containing a nucleic acid such as RNA. In addition, the organic compound C may be a polymer other than a biopolymer.

[0043] The active ingredient may further contain other compounds or materials that function as drugs together with the organic compound C. Examples of drugs include herbicides, weed suppressants, insecticides, fungicides, plant growth regulators, fertilizers, leaf burn preventives, coloring agents, activators, deodorants, repellents, etc. These drugs can be used, for example, as agricultural chemicals for agriculture, forestry, or horticulture, or as horticultural drugs.

[0044] Examples of herbicides include 2,4-PA, MCP, MCPB, MCPA thioethyl (phenothiol), chomeprop, napropanilide, CNP, chlomethoxynil, biphenox, MCC, bensulide, esprocarb, molinate, dimepiperate, DCPA, butachlor, pretilachlor, bromobutide, mefenacet, dimefuron, simetryn, prometryn, dimethametryn, bentazone, oxadiazon, pyrazolate, pyracloxyfen, benzofenap, trifluralin, piperophos, ACN, bensulfuron-methyl, and the like.

[0045] Examples of weed suppressants include bispyribac sodium salt and the like.

[0046] Examples of insecticides include fenthion, MEP, ECP, pyrimiphos-methyl, diazinon, isoxathion, pyridafenthion, florpyrifos-methyl, chlorpyrifos, ESP, bamidothion, profenofos, malathion, PAP, dimethoate, formothion, thiometone, ethylthiometone, fosalon, PMP, DMTP, prothiofos, sulprofos, pyraclofos, DDVP, and monocloto. Phos, BRP, CVMP, Dimethylvinphos, CVP, Propaphos, Acephate, Isofenphos, Salitho, DEP, EPN, Ethion, NAC, MTMC, MIPC, BPMC, PHC, MPMC, XMC, Ethiofencarb, Bendiocarb, Pyrimikab, Carbosulfan, Benfuracarb, Methomyl, Thiodicarb, Aranicarb, Allethrin, Resmethrin, Permethrin, Cyper Examples include metrine, cyhalothrin, cyfluthrin, fenpropathrin, tralomethrin, cycloprothrin, fenvalerate, flucitrinate, fluvalinate, etofenprox, cartap, thiocyclam, bensultap, diflubenzuron, teflubenzuron, chlorfluazurone, buflofezin, phenoxycarb, pyrethrum, deris, nicotine sulfate, machine oil, rapeseed oil, CPCBS, kelthane, chlorbenzilate, phenisobromolate, tetradiphon, BPPS, quinoxaline, amitraz, benzomate, phenothiocarb, hexythiazox, dienochlor, fenpyroximate, fluazinam, pyridaben, clofentezin, DPC, polynaphthine complex, milbemectin, DCIP, dazomet, benzoepin, metaldehyde, BT, and fentrothion.

[0047] Examples of fungicides include kasugamycin, benomyl, thiabendazole, thiophanate-methyl, thiram, prochloraz, trifumizole, ipconazole, basic copper chloride, basic copper sulfate, cupric hydroxide, copper nonylphenolsulfonate, DBEDC, copper terephthalate, inorganic sulfur, zineb, maneb, manzeb, ambam, polycarbamate, organonic acid, propineb, diram, thiadiazine, captan, sulfenic acid derivatives, TPN, phthalide, IBP, EDDP, tolclophosmethyl, pyrazophos, fosetyl, carbendazole, diethofencarb, iprodione, vinclozoline, procymidone, fluorimide, oxycarboxyne, mepronil, flutolanil, tecrophthalam, triclamide, pencyclon, and meta Examples include Laxyl, Oxadixyl, Triadimefon, Vitertanol, Mycrobutanil, Hexaconazole, Propiconazole, Phenalimol, Pyriphenox, Triforine, Blastocidine S, Polyoxin, Validamycin, Streptomycin, Oxytetracycline, Mildiomycin, PCNB, Hydroxyisoxazole, Eclomazole, Chloroneb, Metasulfocarb, Methylisothiocyanate, Organic Arsenic, Zinc Sulfate, Dithianone, Benzothiazole, Quinoxaline derivatives, CNA, Dimethirimol, Diclomazine, Triazine, Felimzon, Fluazinam, Probenazole, Isoprothiolane, Tricyclazole, Pyrroquilon, Oxolinic Acid, Iminocdazine Acetate, and Imibenconazole.

[0048] Examples of plant growth regulators include inabenfide, oxyethylenedocosanol, nicotinamide, benzylaminopurine, indolebutyric acid and its derivatives, indoleacetic acid derivatives, 1-naphthylacetamide, 4-CPA, gibberellin, cloxifonac, forchlorfenuron, paclobutrazol, uniconazole, daminozide, chlormecote, mepicote chloride, flurprimidol, prohexadione calcium salt, wax, oxyquinoline sulfate, abscisic acid, calcium chloride, etephon, and calcium peroxide.

[0049] Examples of fertilizers include oxamide, crotonylidene diurea (CDU), isobutylidene diurea (IB), urea-formaldehyde, fused phosphate fertilizer, mixed phosphate fertilizer, by-product lime fertilizer, calcium carbonate fertilizer, mixed lime fertilizer, mineral silicate fertilizer, other silicate fertilizers, magnesium hydroxide fertilizer, by-product magnesium fertilizer, processed magnesium fertilizer, mineral manganese fertilizer, fused trace element fertilizer, calcium oxide, calcium hydroxide, oil cake, rice bran, cut grass, wood ash, fish meal, dried sardines, compost, horse manure, cow manure, chicken manure, human waste, bone meal, meat and bone meal, stable manure, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, urea, calcium cyanamide, potassium nitrate, superphosphate, potassium dihydrogen phosphate, potassium chloride, potassium sulfate, and potassium carbonate.

[0050] Leaf burn inhibitors are chemicals that can prevent sunburn in plants being grown, and are also called sunscreens or ultraviolet scattering agents. Examples of leaf burn inhibitors include metal oxides, 4-aminobenzoic acid, padimate O, ensulizol, dioxybenzone, oxybenzone, octocrylene, ethylhexyl methoxycinnamate, diethylamino hydroxybenzoyl hexyl benzoate, terephthalylidene dicamphor sulfonic acid, drometrizole trisiloxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, ferulic acid, surisobenzone, avobenzone, ecamsul, enzacamen, benzophenone, butylparaben, and ketoprofen. Examples of metal oxides include kaolin, titanium dioxide, zinc oxide, and cerium oxide.

[0051] Examples of vitality enhancers include choline, fulvic acid, amino acids, minerals, and ferrous ions.

[0052] Examples of deodorizers include betaine compounds, silica gel, and fragrances.

[0053] Examples of repellents include camphor, naphthalene, paradichlorobenzene, pyrethroids, DEET, and picaridin.

[0054] The content of the active ingredient in the retaining layer 2 is not particularly limited, and may be, for example, 0.01 ppb by weight or more, 0.1 ppb by weight or more, 1.0 ppb by weight or more, 0.01 ppm by weight or more, 0.1 ppm by weight or more, and even 1.0 ppm by weight or more. The content of the active ingredient may, in some cases, be 0.01% by weight or more, 0.1% by weight or more, 1.0% by weight or more, 10% by weight or more, 30% by weight or more, and even 50% by weight or more. The upper limit of the content of the active ingredient is, for example, 80% by weight or less. The content of the active ingredient may, in some cases, be 1.0% by weight or less, and may be 0.01% by weight or less.

[0055] A porous filler is a filler having a porous structure. With a porous filler, the migration speed of the active ingredient from the retaining layer 2 to the target object tends to increase. It is preferable that the porous filler is dispersed in the retaining layer 2. The porous fillers may be spaced apart from each other in the retaining layer 2, or they may be partially aggregated.

[0056] In porous fillers, the shape of the pores is not particularly limited. Porous fillers may have continuous pores formed in a three-dimensional manner, or they may have independent pores. It is preferable that porous fillers have through pores that penetrate the porous filler.

[0057] The average pore diameter of the porous filler is, for example, 500 nm or less, and may be 200 nm or less, 150 nm or less, 100 nm or less, 80 nm or less, 50 nm or less, or even 40 nm or less. The lower limit of the average pore diameter of the porous filler is, for example, 5 nm or more, and may be 10 nm or more, or even 20 nm or more. When the average pore diameter of the porous filler is within the above range, the migration speed of the active ingredient from the retaining layer 2 to the target object tends to increase.

[0058] The median pore diameter of the porous filler is, for example, 500 nm or less, and may also be 200 nm or less, 150 nm or less, 100 nm or less, 80 nm or less, 50 nm or less, or even 40 nm or less. The lower limit of the median pore diameter of the porous filler is, for example, 5 nm or more, and may also be 10 nm or more, or even 20 nm or more. When the median pore diameter of the porous filler is within the above range, the migration speed of the active ingredient from the retaining layer 2 to the target object tends to increase.

[0059] The average and median pore diameters of porous fillers can be determined by the following method. First, the porous filler is subjected to gas adsorption using nitrogen gas. Before performing the gas adsorption method, it is preferable to pre-dry the porous filler. The adsorption isotherm data obtained by the gas adsorption method is converted using the BJH (Barrett-Joyner-Halenda) method. The diameters of multiple pores are calculated from the obtained pore diameter distribution. The average value of the obtained calculated values ​​can be considered as the average pore diameter, and the median value can be considered as the median pore diameter.

[0060] The porosity of the porous filler is not particularly limited and may be, for example, 1% to 90% or 10% to 80%.

[0061] The shape of the porous filler can be particulate, fibrous, etc., and particulate is preferred. In this specification, particulate includes spherical, ellipsoidal, and flaky shapes. The average particle diameter of the porous filler is, for example, 30 μm or less, and may be 10 μm or less, 8 μm or less, or even 5 μm or less. The lower limit of the average particle diameter of the porous filler is, for example, 1 nm or more, and may be 10 nm or more, 50 nm or more, 100 nm or more, 500 nm or more, or even 1 μm or more. In this specification, the average particle diameter of the porous filler means the volume-based median diameter (D50) measured by laser diffraction / scattering.

[0062] The porous filler preferably contains an inorganic material. Examples of inorganic materials include carbon materials such as carbon; silicon materials such as silica and silicate compounds; minerals such as clay minerals; and zeolites. The porous filler preferably contains at least one selected from the group consisting of carbon materials and silicon materials.

[0063] Specific examples of porous fillers containing carbon materials include porous carbon. Commercially available porous carbon products include the "Cnovel" series from Toyo Tanso Co., Ltd. Specific examples of porous fillers containing silicon materials include porous silica. Commercially available porous silica products include the H series and L series of "Sunsphere" from AGC SI-TEC Co., Ltd.

[0064] The content of the porous filler in the retaining layer 2 is, for example, 0.1% by weight or more, and may be 1% by weight or more, 5% by weight or more, or even 10% by weight or more. The higher the content of the porous filler, the more likely it is that the migration speed of the active ingredient from the retaining layer 2 to the target object will increase. From the viewpoint of easily manufacturing the retaining layer 2, the upper limit of the content of the porous filler is, for example, 50% by weight or less, and may be 40% by weight or less.

[0065] The retaining layer 2 preferably further contains polymer P that supports the active ingredient and porous filler. Details such as the composition of polymer P will be described later. As an example, if the retaining layer 2 is formed from an emulsion-based resin composition described later, the retaining layer 2 preferably contains polymer P particles derived from the emulsion-based resin composition. In this case, the active ingredient may be retained in the spaces between the polymer P particles and porous filler. In this specification, "emulsion-based composition" means a liquid containing a dispersion medium and a polymer emulsified in the dispersion medium. The retaining layer 2 may have a matrix containing polymer P, in which the active ingredient and porous filler may be dispersed.

[0066] The polymer P content in the retaining layer 2 is, for example, 30% by weight or more, and may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or even 90% by weight or more. The upper limit of the polymer P content is, for example, 99% by weight or less, and may be 95% by weight or less.

[0067] The retaining layer 2 may further contain other components besides the active ingredient, porous filler, and polymer P. These other components include cell transfection agents to promote the introduction of the active ingredient (especially organic compound C) into the cells of a target object (e.g., a plant); tackifiers, etc. Any cell transfection agent can be selected as long as it does not inhibit the function of the active ingredient, but examples include calcium phosphate, cationic lipids, cationic peptides such as polylysine and polyornithine and their derivatives, polysaccharides such as cyclodextrin and chitosan, cationic polymers such as histones and collagen, and carbohydrate polymers such as diethylaminoethyl-dextran.

[0068] Examples of tackifiers include terpene-based tackifiers, terpene-phenol-based tackifiers, rosin-based tackifiers, and styrene-based tackifiers.

[0069] The content of other components in the retaining layer 2 is not particularly limited, and is, for example, 0.01% by weight to 10% by weight.

[0070] The thickness of the retaining layer 2 can be adjusted as appropriate, taking into consideration the amount of active ingredient and the ease with which the active ingredient is released. The thickness of the retaining layer 2 is preferably greater than the average particle size of the porous filler, for example, 10 μm to 1000 μm, and may be 100 μm or less.

[0071] The retaining layer 2 preferably swells when it comes into contact with water, and it is preferable that the swelling rate is appropriately adjusted depending on the type of active ingredient.

[0072] The retaining layer 2 is preferably formed from an emulsion-based resin composition. The emulsion-based resin composition is a liquid containing a dispersion medium and a polymer P1 emulsified in the dispersion medium. The polymer P contained in the retaining layer 2 may be the polymer P1 itself in the emulsion-based resin composition, or it may be a crosslinked polymer P1 (crosslinked product). The emulsion-based resin composition preferably further contains the above-mentioned active ingredients and porous fillers, and may further contain other components mentioned above. The emulsion-based resin composition may also be an adhesive composition that forms the retaining layer 2, which can function as an adhesive layer.

[0073] In an emulsion-based resin composition, polymer P1 is emulsified in a dispersion medium. In other words, the emulsion-based resin composition contains particles of polymer P1. These particles may not be aggregated in the dispersion medium and may exist as single particles (primary particles), or they may aggregate in the dispersion medium to form aggregates. These particles may be of a core-shell type, having a core and a shell covering the core.

[0074] The polymer P1 in the emulsion resin composition may be a homopolymer or a copolymer. Examples of copolymers include random copolymers, block copolymers, and graft copolymers. The emulsion resin composition may contain two or more polymers P1.

[0075] The emulsion resin composition is not particularly limited, but typically includes a (meth)acrylic polymer as polymer P1. In this specification, (meth)acrylic means acrylic and / or methacrylic. (Meth)acrylate means acrylate and / or methacrylate.

[0076] (Meth)acrylic polymers contain, for example, constituent units derived from alkyl (meth)acrylates. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isoamyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, cyclopentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate. Examples of alkyl esters of (meth)acrylic acid having 1 to 20 carbon atoms include acrylate, cyclooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, undecyl (meth)acrylate, isoundecyl (meth)acrylate, isomiristyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-pentadecyl (meth)acrylate, n-octadecyl (meth)acrylate, n-nonadecyl (meth)acrylate, and n-eicosyl (meth)acrylate. The number of carbon atoms in the alkyl ester is preferably 1 to 12, and more preferably 1 to 8. There may be only one alkyl (meth)acrylate or two or more.

[0077] The alkyl (meth)acrylate preferably includes, for example, 2-ethylhexyl (meth)acrylate, and more preferably 2-ethylhexyl acrylate (2EHA).

[0078] In (meth)acrylic polymers, the content of constituent units derived from alkyl (meth)acrylate is, for example, 50% to 99.9% by weight, and may be 70% to 99% by weight, 80% to 98% by weight, or even 90% to 97% by weight.

[0079] The (meth)acrylic polymer may contain structural units derived from other monomers copolymerizable with alkyl (meth)acrylates. Examples of other monomers include carboxyl group-containing monomers, ether group-containing monomers, and silane monomers. There may be only one other monomer or two or more.

[0080] (Meth)acrylic polymers preferably contain structural units derived from carboxyl group-containing monomers. These structural units can contribute to the stabilization of polymer P1 particles in emulsion resin compositions. Carboxyl group-containing monomers are compounds that contain a carboxyl group in their structure and also contain polymerizable unsaturated double bonds such as (meth)acryloyl groups and vinyl groups. Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid, with acrylic acid (AA) being preferred.

[0081] (Meth)acrylic polymers may contain structural units derived from ether group-containing monomers. Ether group-containing monomers are compounds that contain an ether group in their structure and also contain polymerizable unsaturated double bonds such as (meth)acryloyl groups and vinyl groups. The ether group-containing monomer is preferably an alkoxy group-containing monomer. Examples of alkoxy group-containing monomers include alkylene oxide adducts. Examples of alkylene oxide adducts include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate, with 2-methoxyethyl acrylate (MEA) being preferred.

[0082] The (meth)acrylic polymer preferably contains structural units derived from silane monomers. The silane monomer is a radical polymerizable compound having a silicon atom, and is preferably a silane compound having a (meth)acryloyl group. The silane monomer is even more preferably having an alkoxysilyl group. Examples of silane monomers include 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 10-(meth)acryloyloxydecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, and 8-vinyloctyltriethoxysilane.

[0083] Silane monomers typically undergo hydrolysis during emulsification and / or emulsion polymerization in the presence of water, forming silanol groups (-SiOH). That is, when a (meth)acrylic polymer is synthesized using a silane monomer in the presence of water, the constituent units derived from the silane monomer have, for example, silanol groups. In this case, when preparing the retaining layer 2 from the emulsion resin composition, the silanol groups undergo a condensation reaction, causing the (meth)acrylic polymer to crosslink (silanol crosslinking). This method forms a structure in the retaining layer 2 where multiple polymer P1 particles are crosslinked. This structure allows for appropriate adjustment of the distance between polymer P1 particles, making it easier to control the retention and release of active ingredients (especially organic compounds C).

[0084] Note that other monomers are not limited to those mentioned above. Other monomers include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol (meth)acrylamide, N-hydroxy(meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, (4-hydroxymethylcyclohexyl)methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acrylo Sulfo group-containing monomers such as yloxynaphthalene sulfonic acid; phosphate group-containing monomers such as 2-hydroxyethyl (meth)acroyl phosphate; (N-substituted) amide monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide; (meth)acrylate aminoethyl, (meth)acrylate N,N-dimethylaminoethyl, (meth)acrylate t-butylaminoethyl (meth)acrylate aminoalkyl monomers such as tyl; (meth)acrylate alkoxyalkyl monomers; maleimide monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, and N-phenyl maleimide; itaconimide monomers such as N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, and N-lauryl itaconimide;Succinimide monomers such as N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyoctamethylenesuccinimide; vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinyl carboxylic acid amides, styrene, α-methylstyrene, and N-vinylcaprolactam; cyano(meth)acrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate; glycol-based acrylics such as polypropylene glycol (meth)acrylate, methoxyethyl glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate. Acrylic ester monomers; acrylic acid ester monomers having heterocycles, halogen atoms, silicon atoms, etc., such as tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, and silicone (meth)acrylate; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di(meth)acrylate, hexyl di(meth)acrylate, etc.; olefin monomers such as isoprene, dibutadiene, and isobutylene; vinyl ether monomers such as vinyl ether, etc.

[0085] In (meth)acrylic polymers, the content of constituent units derived from other monomers may be greater than, for example, 0% by weight, and may be 0.1% to 50% by weight, 1% to 30% by weight, 2% to 20% by weight, or even 3% to 10% by weight.

[0086] In (meth)acrylic polymers, the content of constituent units derived from carboxyl group-containing monomers is, for example, 0.1% by weight or more, and may be 1% by weight or more, or even 2% by weight or more. This content is, for example, 25% by weight or less, and may be 20% by weight or less, 10% by weight or less, 5% by weight or less, or even 3% by weight or less. When this content is low, the migration speed of the active ingredient from the retaining layer 2 to the target object tends to increase.

[0087] In (meth)acrylic polymers, the content of constituent units derived from ether group-containing monomers is, for example, 0.1% by weight or more, and may be 1% by weight or more, 3% by weight or more, 5% by weight or more, or even 8% by weight or more. This content may be, for example, 25% by weight or less, 20% by weight or less, or even 15% by weight or less. Note that (meth)acrylic polymers do not necessarily have to contain constituent units derived from ether group-containing monomers.

[0088] In (meth)acrylic polymers, the content of constituent units derived from silane monomers is, for example, 0.01% by weight or more. This content may be, for example, 10% by weight or less, 1% by weight or less, or even 0.1% by weight or less.

[0089] The glass transition temperature (Tg) of (meth)acrylic polymers is theoretically calculated using the FOX formula to be, for example, -10°C to 30°C, but may also be -5°C to 20°C, 0°C to 15°C, or even 5°C to 10°C.

[0090] The weight-average molecular weight of (meth)acrylic polymers is, for example, 1,000 to 1,000,000, and may also be 5,000 to 5,000,000, 10,000 to 1,000,000, or even 50,000 to 800,000. The weight-average molecular weight of (meth)acrylic polymers can be controlled by the amount of polymerization initiators, chain transfer agents, emulsifiers, etc. used during polymerization, as well as the reaction conditions.

[0091] (Meth)acrylic polymers can be synthesized by emulsion polymerization using emulsions of monomers as raw materials. In emulsion polymerization, emulsifiers (surfactants), polymerization initiators, and, if necessary, chain transfer agents can be used as appropriate. Methods of emulsion polymerization include the batch method (batch polymerization method), monomer dropwise addition method, and monomer emulsion dropwise addition method. In the monomer dropwise addition method, continuous dropwise addition or divided dropwise addition method can be appropriately selected. These methods can be combined as appropriate. The reaction conditions for emulsion polymerization can be appropriately adjusted according to the monomer group, etc. For example, the polymerization temperature is 40°C to 95°C and the polymerization time is 30 minutes to 24 hours.

[0092] Examples of polymerization initiators include azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057); persulfates such as potassium persulfate and ammonium persulfate; di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di- Examples of peroxide initiators include sec-butyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di(t-hexyl peroxy)cyclohexane, t-butyl hydroperoxide, and hydrogen peroxide; redox initiators combining peroxides and reducing agents, such as combinations of persulfates and sodium bisulfite, and combinations of peroxides and sodium ascorbate. The polymerization initiator may be one type or two or more types.

[0093] The amount of polymerization initiator used is, for example, 0.005 parts by weight to 1 part by weight, or even 0.02 parts by weight to 0.5 parts by weight, per 100 parts by weight of monomers.

[0094] Examples of chain transfer agents include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be one type or two or more types.

[0095] The amount of chain transfer agent used is, for example, 0.1 parts by weight or less per 100 parts by weight of monomer group.

[0096] Examples of emulsifiers include nonreactive surfactants commonly used in emulsion polymerization. Examples of nonreactive surfactants include anionic nonreactive surfactants and nonionic nonreactive surfactants. Specific examples of anionic nonreactive surfactants include higher fatty acid salts such as sodium oleate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate; polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate; alkyl sulfosuccinate salts and their derivatives such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, and sodium polyoxyethylene lauryl sulfosuccinate; and polyoxyethylene distyleninated phenyl ether sulfate salts. Specific examples of nonionic, nonreactive surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; glycerin higher fatty acid esters such as oleic acid monoglyceride and stearate monoglyceride; polyoxyethylene polyoxypropylene block copolymer and polyoxyethylene distyrenated phenyl ether.

[0097] In addition to non-reactive surfactants, other emulsifiers include, for example, reactive surfactants having ethylenically unsaturated double bonds (radical polymerizable functional groups). Examples of reactive surfactants include anionic reactive surfactants obtained by introducing radical polymerizable functional groups such as propenyl groups or allyl ether groups into the above-mentioned anionic non-reactive surfactants, and nonionic reactive surfactants obtained by introducing radical polymerizable functional groups such as propenyl groups or allyl ether groups into the above-mentioned nonionic non-reactive surfactants. Commercially available reactive surfactants can also be used. Specific examples of anionic reactive surfactants include, for example, alkyl ether surfactants (commercial products include, for example, Aqualon KH-05, KH-10, KH-20 from Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N from ADEKA Corporation, and Latemul PD-104 from Kao Corporation); sulfosuccinate surfactants (commercial products include, for example, Latemul S-120, S-120A, S-180P, S-180A from Kao Corporation, and Eleminol JS-20 from Sanyo Chemical Industries, Ltd.); alkylphenyl ether surfactants or alkylphenyl ester surfactants (commercial products include, for example, Aqualon H-2855A, H-3 from Daiichi Kogyo Seiyaku Co., Ltd.) Examples include 855B, H-3855C, H-3856, HS-05, HS-10, HS-20, HS-30, HS-1025, BC-05, BC-10, BC-20, Adekarya Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N manufactured by ADEKA Corporation; (meth)acrylate sulfate ester surfactants (commercial products include, for example, Antox MS-60 and MS-2N manufactured by Nippon Emulsifier Co., Ltd., and Eleminol RS-30 manufactured by Sanyo Chemical Industries, Ltd.); and phosphate ester surfactants (commercial products include, for example, H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Adekarya Soap PP-70 manufactured by ADEKA Corporation).Specific examples of nonionic reactive surfactants include alkyl ether surfactants (commercial products such as Adekarya Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation, and Latemul PD-420, PD-430, PD-450 manufactured by Kao Corporation); alkylphenyl ether surfactants or alkylphenyl ester surfactants (commercial products such as Aqualon RN-10, RN-20, RN-30, RN-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Adekarya Soap NE-10, NE-20, NE-30, NE-40 manufactured by ADEKA Corporation); and (meth)acrylate sulfate ester surfactants (commercial products such as RMA-564, RMA-568, RMA-1114 manufactured by Nippon Emulsifier Co., Ltd.). Reactive surfactants are preferred as emulsifiers, and anionic reactive surfactants are more preferred. The emulsifier may be one type or two or more types.

[0098] The amount of emulsifier used is, for example, 0.1 to 10 parts by weight, or 1 to 5 parts by weight, per 100 parts by weight of the monomer group.

[0099] The dispersion medium used in emulsion polymerization preferably contains water. The dispersion medium may contain an organic solvent instead of water, or together with water. The amount of dispersion medium used is, for example, 30 to 80 parts by weight, or 40 to 70 parts by weight, per 100 parts by weight of monomer group.

[0100] The content of the polymer P1 in the emulsion-based resin composition is not particularly limited, and is, for example, 10% to 90% by weight.

[0101] In an emulsion-based resin composition, the average particle diameter of polymer P1 particles may be, for example, 100 nm or more, 120 nm or more, or even 200 nm or more. The upper limit of the average particle diameter of polymer P1 particles may be, for example, 500 nm or less, or 300 nm or less. In this specification, the average particle diameter of the polymer refers to the volume-based median diameter (D50) measured by laser diffraction / scattering.

[0102] The emulsion resin composition preferably contains water as a dispersion medium. The emulsion resin composition is, for example, an oil-in-water (O / W) emulsion. The emulsion resin composition may contain an organic solvent as a dispersion medium, either in place of water or together with water. The content of the dispersion medium in the emulsion resin composition is not particularly limited, and is, for example, 10% to 90% by weight.

[0103] The emulsion resin composition may further contain a crosslinking agent. Examples of crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and chelate-based crosslinking agents. In cases where the polymer P1 ((meth)acrylic polymer) contained in the emulsion resin composition can undergo the silanol crosslinking described above, the emulsion resin composition may not contain a crosslinking agent.

[0104] The emulsion resin composition may further contain a pH adjuster. Examples of pH adjusters include hydroxides such as potassium hydroxide; and ammonia.

[0105] As described above, the emulsion resin composition preferably further contains a porous filler. The amount of porous filler is, for example, 0.1 parts by weight or more per 100 parts by weight of polymer P1, and may be 1 part by weight or more, 5 parts by weight or more, or even 10 parts by weight or more. The upper limit of the amount of porous filler is, for example, 70 parts by weight or less per 100 parts by weight of polymer P1, and may be 50 parts by weight or less, or even 40 parts by weight or less.

[0106] As described above, the emulsion resin composition preferably further contains an active ingredient. The amount of the active ingredient is, for example, 1.0 × 10⁶ per 100 parts by weight of polymer P1. -10 It is greater than the weight portion, and 1.0 × 10 -9 Weight part or more, 1.0 x 10 -8 Weights above, and even 1.0 x 10 -7It may be more than parts by weight. The upper limit of the amount of active ingredient is, for example, 100 parts by weight or less per 100 parts by weight of polymer P1, 10 parts by weight or less, 1 part by weight or less, 0.1 parts by weight or less, 0.01 parts by weight or less, 1.0 × 10 -3 Below the weight unit, and furthermore 1.0 x 10 -4 It may be less than or equal to the weight.

[0107] (Other components) The adhesive 10 of this embodiment may further comprise other components besides the base material 1 and the retaining layer 2. For example, the adhesive 10 may include a release liner disposed on the surface of the retaining layer 2 as another component. In this case, the adhesive 10 can be used by peeling off the release liner and then attaching the retaining layer 2 to the object.

[0108] (Method for manufacturing the patch) The method for manufacturing the patch 10 of this embodiment is not particularly limited. A preferred example of the method for manufacturing the patch 10 is described below. First, an emulsion-based resin composition containing an active ingredient and a porous filler is applied to the substrate 1 to form a coating film. The method for applying the emulsion-based resin composition is not particularly limited, and for example, a spin coating method or a dip coating method can be used. The emulsion-based resin composition may also be applied using a wire bar or the like.

[0109] Next, the retaining layer 2 is formed by drying the coated film. This allows the adhesive patch 10 to be manufactured. The drying of the coated film can be carried out, for example, under heating conditions. The heating temperature of the coated film is, for example, 50°C or higher, and may be 100°C or higher. The heating time of the coated film is, for example, 1 minute or more. When using active ingredients that may decompose, such as nucleic acids, the drying of the coated film may be carried out under conditions of room temperature (25°C) or lower.

[0110] (Method of using the patch) The patch 10 of this embodiment can be used by attaching it to an object via the retaining layer 2. The object to which the patch 10 is attached is typically a plant. In other words, the patch 10 of this embodiment is a patch used on plants (plant patch). The patch 10 can be used by attaching it to, for example, the leaves, stems (or trunks) or cross-sections of plants. In addition, if necessary, the surface of the plant may be treated by scratching or making holes in it before attaching the patch 10. This treatment can promote the uptake of the active ingredients by the plant. The above treatment is not particularly limited, but may include physical treatment using blades or drills, electrical treatment, pressurization treatment, heating treatment, etc. The object to which the patch 10 is attached may, in some cases, be an animal (especially a human).

[0111] Furthermore, if the target object is a plant, applying the adhesive patch 10 causes, for example, some of the water absorbed from the plant's xylem to move into the retaining layer 2. This causes the retaining layer 2 to swell. When the retaining layer 2 swells, the spaces between the polymer P particles within this layer expand, making it easier for the active ingredient to move into the plant. To sufficiently swell the retaining layer 2, water may be sprayed onto the adhesive patch 10 from the outside while it is attached to the target object.

[0112] <Modified Forms of the Adhesive> The configuration of the adhesive patch 10 is not limited to that shown in Figure 1. As shown in Figure 2, the modified form of the adhesive patch 11 comprises a base material 1, a retaining layer 2, and an adhesive layer 3 in this order in the lamination direction. The retaining layer 2 is a layer that holds the active ingredient and may be in contact with the base material 1 and the adhesive layer 3, respectively. In this embodiment, the active ingredient held by the retaining layer 2 contains an organic compound C with a weight-average molecular weight of 1000 or more. At least one selected from the group consisting of the retaining layer 2 and the adhesive layer 3 contains a porous filler.

[0113] In this embodiment, the patch 11 is configured such that when the adhesive layer 3 is applied to an object (e.g., a plant), the active ingredient gradually moves from the retaining layer 2 to the object through the adhesive layer 3. Similar to the patch 10, the patch 11 functions as a sustained-release sheet that gradually releases the active ingredient to the object.

[0114] In the patch 11 of this embodiment, at least one selected from the group consisting of the retaining layer 2 and the adhesive layer 3 contains a porous filler, which facilitates the release of the active ingredient from the patch 11 to the target object, and tends to supply a sufficient amount of the active ingredient to the target object even when the molecular weight of the active ingredient is large.

[0115] In the adhesive patch 11, the base material 1 and the retaining layer 2 can be the same as those described above for the adhesive patch 10. However, if the adhesive layer 3 contains a porous filler, the retaining layer 2 does not necessarily need to contain a porous filler.

[0116] In the patch 11, the adhesive layer 3 has a surface exposed to the outside of the patch 11, and the patch 11 can be attached to an object via this surface. The adhesive layer 3 is configured so that when the patch 11 is attached to an object, the active ingredient can be transferred from the retaining layer 2 to the object through the adhesive layer 3. Preferably, the adhesive layer 3 does not contain substantially any active ingredient until the patch 11 is attached to an object. However, the adhesive layer 3 may contain a small amount of active ingredient derived from the retaining layer 2.

[0117] The adhesive layer 3 preferably contains a porous filler. Examples of porous fillers include those described above for the adhesive patch 10. However, if the retaining layer 2 contains a porous filler, the adhesive layer 3 does not need to contain a porous filler. Furthermore, from the viewpoint of increasing the migration speed of the active ingredient from the retaining layer 2 to the object, it is preferable that both the retaining layer 2 and the adhesive layer 3 contain a porous filler.

[0118] The content of porous filler in the adhesive layer 3 is, for example, 0.1% by weight or more, and may be 1% by weight or more, 5% by weight or more, or even 10% by weight or more. The higher the content of porous filler, the more likely it is that the migration speed of the active ingredient from the retaining layer 2 to the object will increase. From the viewpoint of easily manufacturing the adhesive layer 3, the upper limit of the content of porous filler is, for example, 50% by weight or less, and may be 40% by weight or less.

[0119] The adhesive layer 3 preferably contains polymer Q that supports the porous filler. For example, if the adhesive layer 3 is formed from an emulsion-based adhesive composition described later, the adhesive layer 3 preferably contains particles of polymer Q derived from the emulsion-based adhesive composition. The adhesive layer 3 may also have a matrix containing polymer Q, in which the porous filler is dispersed.

[0120] The polymer Q content in the adhesive layer 3 is, for example, 30% by weight or more, and may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, and even 90% by weight or more. The upper limit of the polymer Q content is, for example, 99% by weight or less, and may be 95% by weight or less.

[0121] The adhesive layer 3 may further contain other components besides the porous filler and polymer Q. Examples of other components include the tackifiers mentioned above. The content of the other components in the adhesive layer 3 is not particularly limited, and is, for example, 0.01% to 10% by weight.

[0122] The thickness of the adhesive layer 3 is, for example, 5 μm or more, and may be 10 μm or more, or even 15 μm or more, from the viewpoint of improving the peel strength against the target object. The upper limit of the thickness of the adhesive layer 3 can be appropriately adjusted considering the ease of release of the active ingredients, etc. It is preferable that the thickness of the adhesive layer 3 is greater than the average particle size of the porous filler.

[0123] The adhesive layer 3 preferably swells when it comes into contact with water, for example, and the swelling rate is preferably adjusted appropriately depending on the type of active ingredient held in the retaining layer 2.

[0124] The adhesive layer 3 is preferably formed from an emulsion-based adhesive composition. The emulsion-based adhesive composition is a liquid containing a dispersion medium and polymer Q1 emulsified in the dispersion medium. The polymer Q contained in the adhesive layer 3 may be the polymer Q1 itself in the emulsion-based adhesive composition, or it may be a crosslinked polymer Q1 (crosslinked product). The emulsion-based adhesive composition preferably further contains a porous filler and may further contain other components as described above.

[0125] In an emulsion-based adhesive composition, polymer Q1 is emulsified in a dispersion medium. In other words, the emulsion-based adhesive composition contains particles of polymer Q1. These particles may not be aggregated in the dispersion medium and may exist as single particles (primary particles), or they may aggregate in the dispersion medium to form aggregates. These particles may be of a core-shell type, having a core and a shell covering the core.

[0126] The polymer Q1 in the emulsion-type adhesive composition may be a homopolymer or a copolymer. Examples of copolymers include random copolymers, block copolymers, and graft copolymers. The emulsion-type adhesive composition may contain two or more polymers Q1.

[0127] Examples of polymer Q1 in an emulsion-based adhesive composition include those described above for polymer P1 in an emulsion-based resin composition. Polymer Q1 may be the same as or different from polymer P1. Emulsion-based adhesive compositions typically contain a (meth)acrylic polymer as polymer Q1.

[0128] The (meth)acrylic polymer as polymer Q1 includes, for example, structural units derived from alkyl (meth)acrylate esters, and further includes structural units derived from other monomers such as carboxyl group-containing monomers, ether group-containing monomers, and silane monomers. The content of these monomers and each structural unit is as described above for polymer P1.

[0129] The content of the polymer Q1 in the emulsion-based adhesive composition is not particularly limited, and is, for example, 10% to 90% by weight.

[0130] In an emulsion-type adhesive composition, the average particle diameter of polymer Q1 particles is, for example, 100 nm or more, and may be 120 nm or more, or even 200 nm or more. The upper limit of the average particle diameter of polymer Q1 particles is, for example, 500 nm or less, and may be 300 nm or less.

[0131] The emulsion-type adhesive composition preferably contains water as a dispersion medium. The emulsion-type adhesive composition is, for example, an oil-in-water (O / W) type emulsion. The emulsion-type adhesive composition may contain an organic solvent as a dispersion medium, either in place of water or together with water. The content of the dispersion medium in the emulsion-type adhesive composition is not particularly limited, and is, for example, 10% to 90% by weight.

[0132] The emulsion-based adhesive composition may further contain a crosslinking agent. Examples of crosslinking agents include those described above for emulsion-based resin compositions. In cases where polymer Q1 ((meth)acrylic polymer) contained in the emulsion-based adhesive composition can undergo the silanol crosslinking described above, the emulsion-based adhesive composition may not contain a crosslinking agent.

[0133] As described above, the emulsion-type adhesive composition preferably further contains a porous filler. The amount of porous filler is, for example, 0.1 parts by weight or more per 100 parts by weight of polymer Q1, and may be 1 part by weight or more, 5 parts by weight or more, or even 10 parts by weight or more. The upper limit of the amount of porous filler is, for example, 70 parts by weight or less per 100 parts by weight of polymer Q1, and may be 50 parts by weight or less, or even 40 parts by weight or less.

[0134] (Other components) The adhesive 11 of this embodiment may further comprise other components besides the base material 1, the retaining layer 2, and the adhesive layer 3. For example, the adhesive 11 may include a release liner disposed on the surface of the adhesive layer 3 as another component. In this case, the adhesive 11 can be used by peeling off the release liner and then attaching the adhesive layer 3 to the object.

[0135] (Method for Manufacturing the Adhesive) The method for manufacturing the adhesive patch 11 in this embodiment is not particularly limited. A preferred example of the method for manufacturing the adhesive patch 11 is described below. First, a retaining layer 2 is formed on the substrate 1 by the method described above for the adhesive patch 10. Next, an emulsion-based adhesive composition is applied to the retaining layer 2 to form a coating film. The method for applying the emulsion-based adhesive composition can be the same as that described above for the retaining layer 2. Next, an adhesive layer 3 is formed by drying the coating film. This allows the adhesive patch 11 to be manufactured. The drying conditions for the coating film can be the same as those described above for the retaining layer 2.

[0136] The method for manufacturing the adhesive patch 11 is not limited to those described above. For example, the adhesive patch 11 may be manufactured by separately preparing a laminate of the base material 1 and the retaining layer 2, and a laminate of the release liner and the adhesive layer 3, and then bonding these laminates together.

[0137] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0138] (Example 1) First, the following raw materials were placed in a container: 97 parts by weight of 2-ethylhexyl acrylate (2EHA), 3 parts by weight of acrylic acid (AA), 0.01 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3 parts by weight of the anionic reactive surfactant Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.02 parts by weight of the chain transfer agent t-dodecanethiol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 51.7 parts by weight of deionized water. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 2000 rpm for 1 minute under a nitrogen atmosphere, and then stirred for a further 5 minutes at 6000 rpm to prepare a monomer emulsion.

[0139] In a reaction vessel equipped with a condenser, nitrogen inlet tube, thermometer, dropping device, and stirring blade, 51.5 parts by weight of deionized water were added and thoroughly purged with nitrogen while stirring, and then the deionized water was heated to 60°C. After confirming that the temperature had stabilized at 60°C, 0.24 parts by weight of VA-057 (2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, a water-soluble azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd., was added, and 154.7 parts by weight of monomer emulsion were added dropwise over 3 hours. Further aging over 3 hours was performed to obtain an aqueous dispersion of a (meth)acrylic polymer.

[0140] To 10 g of the above aqueous dispersion, 3 g of porous carbon (manufactured by Toyo Tanso Co., Ltd., CNovel MJ(4)010) as a filler was added, and the mixture was stirred at 3,000 rpm for 20 minutes using a disperser mixer (manufactured by Primix Co., Ltd., Lab-Solution). After that, an aqueous potassium hydroxide solution was added, and the mixture was stirred with a stirring rod to adjust the pH to 6-7. The filler was added in the maximum amount possible within the range that would result in a coatable emulsion-type resin composition. Specifically, the amount of filler added was 6 parts by weight per 100 parts by weight of (meth)acrylic polymer contained in the aqueous dispersion.

[0141] Next, 1.8 ng of ribonucleic acid (RNA, base number: approximately 3,000, weight-average molecular weight: approximately 900,000) as an active ingredient was added and stirred with a stirring rod. Then, the mixture was stirred at 2,000 rpm for 1 minute and degassed at 2,200 rpm for 1 minute using a mixer (Sinky Co., Ltd., ARE-310) to obtain an emulsion-type resin composition.

[0142] Next, a polyethylene terephthalate (PET) film (approximately 38 μm thick) was prepared as a substrate. The prepared emulsion-based resin composition was applied to this substrate to obtain a coating film approximately 50 μm thick. The emulsion-based resin composition was applied using a YBA-4 type applicator. Next, a retaining layer (approximately 25 μm thick) was formed by heating and drying the coating film at 50°C for 15 minutes. At this time, the (meth)acrylic polymer contained in the emulsion-based resin composition was crosslinked by a condensation reaction between silanol groups. This obtained the adhesive patch of Example 1, which consists of a substrate and a retaining layer.

[0143] (Examples 2-4) The adhesive patches of Examples 2-4 were obtained by the same method as in Example 1, except that the type and amount of filler used were changed as shown in Table 1. In Examples 2-4, the filler was added in the maximum amount possible within the range where the resulting emulsion-based resin composition had a viscosity suitable for application. The filler used in Example 4 was non-porous.

[0144] [Average Particle Size of Fillers] The average particle size of the fillers used in Examples 1 to 3 was measured by the following method. First, a dispersion of the fillers was prepared. Specifically, the dispersion was prepared by dispersing the fillers in a mixture of water and a nonionic surfactant (Tween 20). The obtained dispersion was set in a laser diffraction particle size analyzer (Microtrac-Bell, MT3300EXII) and the median diameter (D50) of the fillers was measured. This measurement was performed three times, and the average of the obtained measurements was considered to be the average particle size of the fillers. For the filler used in Example 4, the manufacturer's catalog value for the average particle size is shown in Table 1.

[0145] [Average and Median Pore Diameter of Filler] The average pore diameter of the fillers used in Examples 1 to 3 was measured by the following method. First, the filler was degassed (pre-treated) by heating it at 150°C for 6 hours using a pre-treatment device (Microtrac-Bel, BELPREP VACIII). After pre-treatment, the filler was placed in a specific surface area and pore distribution analyzer (Microtrac-Bel, BELSORP MAXII) and measured by nitrogen adsorption. The adsorption isotherms obtained from this measurement were converted using the BJH (Barrett-Joyner-Halenda) method, and the diameters of multiple pores contained in the filler were calculated from the obtained pore diameter distribution. Of the calculated values, the average value was considered as the average pore diameter, and the median value was considered as the median pore diameter.

[0146] [Dissolution Test] Dissolution tests were performed on the transdermal patches of Examples 1-4 using the following method. First, a dilution series was prepared from an mRNA solution of unknown concentration. Real-time PCR (Polymerase Chain Reaction) was performed on the dilution series to determine the Ct value (the number of cycles until the amount of fluorescence due to RNA reaches the threshold). A calibration curve was created based on the obtained results. A 7500Fast (Thermo Fisher Scientific) was used as the real-time PCR instrument.

[0147] In parallel with the above operations, the following operations were performed. First, the surface area of ​​the retaining layer in the patch was 4 cm². 2 The patch was cut to a size of 2 cm x 2 cm to create a test piece. Next, 600 μL of water was dropped into a plastic petri dish, and the patch was placed in the dish so that the surface of the retaining layer was in contact with the water. After 5 hours, the water that was not absorbed by the retaining layer was collected. Real-time PCR was performed on this water to determine the Ct value. Using the calibration curve described above, data on RNA concentration was obtained from the Ct value. From the obtained data, the relative values ​​of RNA concentration for Examples 1 to 3 were determined, with the RNA concentration in Example 4 set to 1.

[0148]

[0149] The abbreviations in Table 1 are as follows: MJ(4)010: Porous carbon (manufactured by Toyo Tanso Co., Ltd., CNovel MJ(4)010) MJ(4)030: Porous carbon (manufactured by Toyo Tanso Co., Ltd., CNovel MJ(4)030) MJ(4)150: Porous carbon (manufactured by Toyo Tanso Co., Ltd., CNovel MJ(4)150) AEROSIL50: Silica particles (non-porous) (manufactured by Nippon Aerosil Co., Ltd., AEROSIL50)

[0150] (Examples 5-7) The adhesive patches of Examples 5-7 were obtained by the same method as in Example 1, except that the type and amount of filler used were changed as shown in Table 2. In Examples 5-6, the filler was added in the maximum amount possible within the range where the resulting emulsion-based resin composition had a viscosity suitable for application. The filler used in Example 7 was non-porous.

[0151] [Average particle size of filler] The average particle size of the fillers used in Examples 5 to 7 was measured using the same method as in Examples 1 to 3.

[0152] [Average and median pore diameter of fillers] The average and median pore diameters of the fillers used in Examples 5 and 6 were measured using the same method as in Examples 1 to 3.

[0153] [Elution Test] Elution tests were performed on Examples 5-7 using the same method as in Examples 1-4, and data on RNA concentration was obtained. From the obtained data, the relative values ​​of RNA concentration in Examples 5 and 6 were determined, with the RNA concentration in Example 7 set to 1.

[0154]

[0155] The abbreviations in Table 2 are as follows: H-33: Porous silica (manufactured by AGC SI-TEC Co., Ltd., Sunsphere H-33) L-31: Porous silica (manufactured by AGC SI-TEC Co., Ltd., Sunsphere L-31) NP-30: Silica particles (non-porous) (manufactured by AGC SI-TEC Co., Ltd., Sunsphere NP-30)

[0156] From the dissolution test results in Table 1, it can be seen that the patches of Examples 1 to 3, in which the retaining layer contains a porous filler, have a higher dissolution rate of the active ingredient compared to the patch of Example 4, and are suitable for releasing active ingredients with a large molecular weight. Similarly, from the dissolution test results in Table 2, it can be seen that the patches of Examples 5 and 6, in which the retaining layer contains a porous filler, have a higher dissolution rate of the active ingredient compared to the patch of Example 7, and are suitable for releasing active ingredients with a large molecular weight.

[0157] The adhesive patch of this embodiment can be used by attaching it to an object such as a plant.

Claims

1. A patch comprising a base material and a retaining layer for holding an active ingredient, wherein the active ingredient contains an organic compound with a weight-average molecular weight of 1000 or more, and the retaining layer contains a porous filler.

2. A patch comprising a base material, a retaining layer for holding an active ingredient, and an adhesive layer, arranged in this order in the lamination direction, wherein the active ingredient comprises an organic compound with a weight-average molecular weight of 1000 or more, and at least one selected from the group consisting of the retaining layer and the adhesive layer contains a porous filler.

3. The patch according to claim 1 or 2, wherein the organic compound includes a biopolymer.

4. The patch according to claim 3, wherein the biopolymer contains nucleic acid.

5. The patch according to claim 4, wherein the nucleic acid comprises ribonucleic acid.

6. The patch according to claim 1 or 2, wherein the average pore diameter of the porous filler is 200 nm or less.

7. The patch according to claim 1 or 2, wherein the average pore diameter of the porous filler is 5 nm or more.

8. The patch according to claim 1 or 2, wherein the median pore size of the porous filler is 10 nm or more.

9. The patch according to claim 1 or 2, wherein the average particle size of the porous filler is 10 μm or less.

10. The adhesive patch according to claim 1 or 2, wherein the porous filler comprises at least one selected from the group consisting of carbon materials and silicon materials.

11. The adhesive patch according to claim 1 or 2, wherein the retaining layer is formed from an emulsion-based resin composition.

12. The adhesive patch according to claim 11, wherein the emulsion-based resin composition comprises a (meth)acrylic polymer.

13. The patch according to claim 12, wherein the (meth)acrylic polymer comprises structural units derived from a carboxyl group-containing monomer.

14. The adhesive patch according to claim 12, wherein the (meth)acrylic polymer comprises structural units derived from silane monomers.

15. The adhesive patch according to claim 11, wherein the emulsion resin composition contains water as a dispersion medium.

16. The patch according to claim 1 or 2, for use on plants.

Images