Organogel

Abstract

An organic gel comprising a high molecular matrix and a plasticizer, a moisture content being less than 1.0 mass% relative to the total amount of the organic gel, the organic gel comprising, as a polymerizable monomer constituting the high molecular matrix, a (meth)acrylate having an alicyclic hydrocarbon in the structure, the plasticizer being a plasticizer comprising at least one selected from the group consisting of an aliphatic hydrocarbon and an aliphatic acid ester and being liquid or paste-like at 25°C, the organic gel having an initial adhesion to a bakelite board of 1.0 N / 20 mm or more, and a retention rate of the adhesion after immersion in water for 1 hour of 90% or more.

Description

Technical Field

[0001] This invention relates to an organic gel. Background Technology

[0002] Gel-like materials possess various properties such as water absorption, swelling, moisturizing, adhesion, conformability, cooling, and conductivity. These properties are fully utilized in a wide range of fields, including medical, cosmetic, electrical, beauty and health instruments, sports, and food.

[0003] Gel-like materials can be broadly classified into hydrogels, in which water is the main solvent, and organic gels, in which organic solvents are the main solvents.

[0004] As a hydrogel, for example, Patent Document 1 discloses a hydrogel containing a polymer matrix, water and a plasticizer, which can suppress the swelling of the gel caused by the infiltration of moisture from the outside, and maintain the initial high adhesive strength by reducing the loss of plasticizer.

[0005] Patent Document 2 discloses a high-strength adhesive polymeric gel formed from a polymer and a polyol. This adhesive gel possesses sufficient adhesive force and tensile strength. Existing technical documents Patent documents

[0006] Patent Document 1: Japanese Patent No. 7037639 Patent Document 2: Japanese Patent No. 5393147 Summary of the Invention The technical problem that the invention aims to solve

[0007] In applications where gel-like materials are applied directly to the skin, excellent water resistance is desirable because the gel-like materials are expected to be directly exposed to water due to bathing, washing of the area around the application site, etc.

[0008] The hydrogel disclosed in Patent Document 1 has a problem with water resistance because it will immediately detach from the skin or machine in water.

[0009] Existing organic gels, due to their high hydrophobicity, exhibit superior water resistance compared to hydrogels, but lack sufficient adhesive strength. While the organic gel disclosed in existing literature 2 improves its adhesive strength, it also swells upon absorbing moisture during exercise, showering, etc., thus compromising both water resistance and the sustainability of its adhesive strength.

[0010] The problem to be solved by the present invention is to provide an organic gel with excellent water resistance, sustained adhesive strength and appearance, and moderate softness. Means for solving technical problems

[0011] The present invention includes the embodiments described below. [1] An organic gel comprising a polymer matrix and a plasticizer, The moisture content relative to the total amount of the above-mentioned organic gel is less than 1.0% by mass. The aforementioned organic gel contains (meth)acrylates having alicyclic hydrocarbons in their structure as polymerizable monomers constituting the aforementioned polymer matrix. The aforementioned plasticizer comprises at least one selected from aliphatic hydrocarbons, fatty acid esters, and silicone oils, and is a liquid or paste-like plasticizer at 25°C. The organic gel has an initial adhesion force of 1.0 N / 20 mm or more to the bakelite board, and retains more than 90% of the adhesion force after immersion in water for 1 hour. [2] According to the organic gel of [1], wherein the above-mentioned (meth)acrylate having an alicyclic hydrocarbon in its structure comprises 4-tert-butylcyclohexyl acrylate. [3] The organic gel according to [1] or [2] further comprises at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers as polymerizable monomers constituting the above-mentioned polymer matrix. [4] The organic gel according to any one of [1] to [3], wherein the amount of the (meth)acrylate having an alicyclic hydrocarbon in the structure is 30% by mass or more relative to the total amount of the polymer matrix. [5] The organic gel according to any one of [1] to [4], wherein the content of the plasticizer is 10 to 60 by mass relative to the total amount of the organic gel. [6] The organic gel according to any one of [1] to [5] has a thickness in the range of 100 μm to 1000 μm. Invention Effects

[0012] According to the present invention, an organic gel with excellent water resistance, long-lasting adhesion and appearance, and moderate softness can be provided. Detailed Implementation

[0013] In this specification, unless otherwise expressly stated or clearly contradicted herein, the singular form includes both the singular and the plural.

[0014] In this specification, "contains" includes the concepts of "substantially constitutes only" and "consisting only of".

[0015] In the numerical ranges described in this specification, the upper or lower limit of a certain range can be arbitrarily combined with the upper or lower limits of other ranges. Furthermore, the upper or lower limit of the numerical ranges described in this specification can be replaced by the values ​​shown in the embodiments or values ​​unambiguously derived from the embodiments. Additionally, in this specification, numerical values ​​connected by "~" refer to a range including the values ​​before and after "~" as the lower and upper limits.

[0016] According to one aspect of the present invention, an organic gel is provided, comprising a polymer matrix and a plasticizer, wherein the moisture content is less than 1.0% by mass relative to the total amount of the organic gel; the organic gel comprises a (meth)acrylate having an alicyclic hydrocarbon in its structure as a polymerizable monomer constituting the polymer matrix; the plasticizer comprises at least one selected from aliphatic hydrocarbons, fatty acid esters and silicone oils, and is a liquid or paste-like plasticizer at 25°C; the organic gel has an initial adhesion force of 1.0 N / 20 mm or more to bakelite boards, and retains an adhesion force of 90% or more after immersion in water for 1 hour.

[0017] polymer matrix There are no particular limitations on the polymer matrix as long as it can form an organic gel.

[0018] The content of the polymer matrix in the organic gel is not particularly limited, but it is preferably in the range of 40 to 90% by mass relative to the total amount of organic gel, more preferably in the range of 50 to 80% by mass, and even more preferably in the range of 60 to 70% by mass.

[0019] The organic gel of the present invention contains (meth)acrylates having an alicyclic hydrocarbon in their structure as polymerizable monomers constituting the polymer matrix. "In their structure" refers to their own structure, that is, the structure of the (meth)acrylate. By including (meth)acrylates having an alicyclic hydrocarbon in their structure as polymerizable monomers constituting the polymer matrix, the exudation of plasticizers can be suppressed, resulting in an organic gel with excellent appearance.

[0020] As a (meth)acrylate having an alicyclic hydrocarbon in its structure, one or more selected from 4-tert-butylcyclohexyl acrylate, isobornyl acrylate, 1,4-cyclohexanediol monoacrylate, and 3,3,5-trimethylcyclohexyl acrylate can be used. From the viewpoint of adhesive strength, one or both of 4-tert-butylcyclohexyl acrylate and 3,3,5-trimethylcyclohexyl acrylate are preferred.

[0021] From the viewpoint of obtaining an organic gel with excellent water resistance, sustained adhesion, and appearance, the amount of (meth)acrylate containing alicyclic hydrocarbons in the structure is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more relative to the total amount of the polymer matrix.

[0022] Similarly, from the viewpoint of obtaining an organic gel with excellent water resistance, adhesive strength and appearance, the content of structural units derived from (meth)acrylates having alicyclic hydrocarbons in the structure is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more relative to the total amount of the polymer matrix.

[0023] Furthermore, from the viewpoint of obtaining an organic gel with excellent water resistance, adhesive strength, and appearance, the amount of (meth)acrylate containing alicyclic hydrocarbons in the structure is preferably in the range of 10 to 90% by mass relative to the total amount of organic gel, more preferably in the range of 40 to 80% by mass, and even more preferably in the range of 50 to 70% by mass.

[0024] Similarly, from the viewpoint of obtaining an organic gel with excellent water resistance, adhesive strength and appearance, the content of structural units derived from (meth)acrylates having alicyclic hydrocarbons in the structure is preferably in the range of 10 to 90% by mass relative to the total amount of organic gel, more preferably in the range of 40 to 80% by mass, and even more preferably in the range of 50 to 70% by mass.

[0025] In one embodiment of the invention, the (meth)acrylate having an alicyclic hydrocarbon in its structure comprises 4-tert-butylcyclohexyl acrylate. From the viewpoint of obtaining an organogel with excellent water resistance, sustained adhesive strength, and appearance, 4-tert-butylcyclohexyl acrylate is preferred.

[0026] In one embodiment of the invention, the organic gel further comprises at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers as a polymerizable monomer constituting the polymer matrix. However, neither the (meth)acrylamide monomers nor the (meth)acrylate monomers include (meth)acrylates having an alicyclic hydrocarbon in their structure.

[0027] By including at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers as polymerizable monomers constituting the polymer matrix in addition to (meth)acrylates having alicyclic hydrocarbons in their structure, the physical properties of organic gels, such as adhesiveness and flexibility, can be adjusted.

[0028] Examples of (meth)acrylamide monomers include: (meth)acrylamide; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and other N,N-dialkyl (meth)acrylamides; N-isopropyl (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, and other N-alkyl (meth)acrylamides; N-ethoxymethyl (meth)acrylamide, N-propoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, N-pentoxymethyl (meth)acrylamide, N-hexyloxymethyl (meth)acrylamide, N-heptoxymethyl (meth)acrylamide, N-octoxymethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-propoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide, and other N-alkoxyalkyl (meth)acrylamides; and their derivatives. Preferably, the acrylamide is selected from one or more of N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, and N-propyl (meth)acrylamide, but is not limited thereto. In a particular preferred embodiment, the (meth)acrylamide monomer comprises one or two monomers selected from N,N-dimethylacrylamide and N,N-diethylacrylamide.

[0029] Examples of (meth)acrylate monomers include alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-pentyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tridecyl (meth)acrylate, n-stearyl (meth)acrylate, etc., but are not limited thereto. In a particular preferred embodiment, the (meth)acrylate monomer comprises one or two monomers selected from n-octyl acrylate and isodecyl acrylate.

[0030] When the organic gel contains at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers, from the viewpoints of water resistance, adhesion persistence and appearance, the amount of at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers is preferably in the range of 1.0 to 60% by mass relative to the total amount of the polymer matrix, more preferably in the range of 5.0 to 50% by mass.

[0031] Furthermore, from the viewpoints of water resistance, adhesion persistence, and appearance, the amount of at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers is preferably in the range of 1.0 to 40% by mass relative to the total amount of organic gel, and more preferably in the range of 3.0 to 30% by mass.

[0032] Crosslinking monomers can be added as monomers constituting the polymer matrix, or they can be omitted. From the viewpoint of the shape retention of the organogel, the addition of crosslinking monomers is preferred.

[0033] As a crosslinking monomer, monomers having two or more polymerizable carbon-carbon double bonds within the molecule are preferred.

[0034] Examples of crosslinking monomers include methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, polyethylene glycol di(meth)acrylate and poly(propylene glycol di(meth)acrylate, polyalkylene glycol dimethacrylates, glycerol di(meth)acrylate, glycerol tri(meth)acrylate and other polyfunctional (meth)acrylamides or polyfunctional (meth)acrylates, polyglycerol poly(meth)acrylates and other polyfunctional (meth)acrylates, tetraallyloxyethane, etc., which may be used in one or in combination of two or more. In a particular preferred embodiment, the crosslinking monomer comprises polyalkylene glycol dimethacrylate.

[0035] There is no particular limitation on the amount of crosslinking monomers. From the viewpoint of the adhesiveness and flexibility of the organic gel, it is preferably in the range of 0.10 to 3.0% by mass relative to the total amount of polymer matrix, and more preferably in the range of 0.50 to 2.0% by mass.

[0036] To form a polymer matrix, a polymerization initiator can be added. The amount of polymerization initiator is not particularly limited, but from the viewpoint of the strength and shape retention of the organic gel, it is preferably in the range of 1.0 to 5.0% by mass relative to the total amount of the polymer matrix, and more preferably in the range of 1.0 to 3.0% by mass.

[0037] The type of polymerization initiator is not particularly limited; it can be a photopolymerization initiator or a thermal polymerization initiator. When molding the organic gel into sheets, a photopolymerization initiator is preferred. Examples of photopolymerization initiators include acetophenone-based polymerization initiators, azo-based polymerization initiators, thioxanone-based polymerization initiators, benzophenone-based polymerization initiators, acylphosphine oxide-based polymerization initiators, oxime ester-based polymerization initiators, benzoin-based polymerization initiators, and benzoin ketal-based polymerization initiators. 2-Hydroxy-2-methylphenylacetone is more preferably used.

[0038] The polymer matrix may further contain components other than those described above without impairing the effects of the present invention. The content and composition of the polymer matrix in the organic gel can be appropriately prepared in a manner that satisfies the numerical ranges of the initial adhesive force, adhesive force retention rate and moisture content mentioned above.

[0039] plasticizer The plasticizer is a plasticizer containing at least one selected from aliphatic hydrocarbons, fatty acid esters, and silicone oils, and is in a liquid or paste state at 25°C. By adding the plasticizer described above, an organic gel with excellent water resistance and moderate elasticity can be obtained.

[0040] Examples of aliphatic hydrocarbons include liquid paraffin, squalane, hydrogenated polyisobutylene, and hydrogenated polydecene. From the viewpoint of obtaining excellent water resistance and moderate elasticity, aliphatic hydrocarbons preferably include one or more selected from liquid paraffin, squalane, hydrogenated polyisobutylene, and hydrogenated polydecene.

[0041] Examples of fatty acid esters include glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid methyl esters. More specifically, examples include castor oil and glyceryl triisostearate. From the viewpoint of obtaining excellent water resistance and moderate elasticity, the fatty acid ester preferably contains one or more selected from glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid methyl esters. More specifically, it is preferable to contain one or both of castor oil and glyceryl triisostearate.

[0042] Examples of silicone oils include linear silicone oils, cyclic silicone oils, methylhydrosilicone oils, branched silicone oils, alkyl-modified silicone oils, alcohol-modified silicone oils, and amino-modified silicone oils. From the viewpoint of obtaining excellent water resistance and moderate elasticity, the silicone oil preferably contains one or more of the following: linear silicone oils, cyclic silicone oils, methylhydrosilicone oils, branched silicone oils, alkyl-modified silicone oils, alcohol-modified silicone oils, and amino-modified silicone oils.

[0043] The content of plasticizer is not particularly limited, but it is preferably in the range of 15 to 120% by mass relative to the total amount of polymer matrix, more preferably in the range of 20 to 120% by mass, even more preferably in the range of 40 to 100% by mass, and particularly preferably in the range of 50 to 80% by mass.

[0044] The content of plasticizer is not particularly limited, but it is preferably in the range of 10 to 60% by mass relative to the total amount of organic gel, more preferably in the range of 25 to 55% by mass, and even more preferably in the range of 35 to 50% by mass.

[0045] The content and composition of plasticizers in organic gels can be appropriately prepared in a manner that satisfies the numerical ranges of the aforementioned initial adhesive force, adhesive force retention rate, and moisture content.

[0046] The organic gel of the present invention has a water content of less than 1.0% by mass. From the viewpoint of hydrolysis, the water content of the organic gel relative to the total amount of organic gel is preferably less than 0.80% by mass, more preferably less than 0.50% by mass, and particularly preferably free of water.

[0047] Moisture content of organic gels The moisture content of organic gels can be determined using the following methods.

[0048] A sample of organic gel of any mass is measured and placed in a vial, which is then sealed with an aluminum cap. The sample is placed in a moisture vaporization apparatus. The vial is then heated to 125°C to vaporize the moisture in the sample, and the mass of the vaporized moisture is measured using a moisture analyzer. The measured mass of vaporized moisture is divided by the measured mass of the organic gel and multiplied by 100. The resulting value is taken as the moisture content (%) of the organic gel. Typically, the moisture content of the organic gel can be determined using the method described in the examples.

[0049] The organic gel of the present invention may contain other components besides those described above, as needed. Examples of such components include: rust inhibitors, mildew inhibitors, antioxidants, defoamers, stabilizers, surfactants, colorants, thickeners, humectants, fragrances, etc.

[0050] Examples of thickeners include dextrin fatty acid esters, polyethylene wax, inorganic fillers, silica particles, and cellulose fibers, but are not limited thereto. In a particular preferred embodiment, the thickener comprises one or more selected from dextrin fatty acid esters, silica particles, and cellulose fibers.

[0051] Examples of moisturizers include, but are not limited to, skin and nail care oils and skin conditioning agents such as shea butter, jojoba oil, apricot kernel oil, almond oil, and olive fruit oil. In a particular preferred embodiment, the moisturizer comprises one or more of shea butter, jojoba oil, and almond oil.

[0052] Examples of fragrances include menthol and essential oils, but are not limited to these. In a particular preferred embodiment, the fragrance comprises one or more selected from menthol and essential oils.

[0053] By achieving an initial adhesion force of 1.0 N / 20 mm or more to the organic gel of the present invention on bakelite boards, and retaining an adhesion force of 90% or more after immersion in water for 1 hour, the adhesive strength exhibits excellent durability, water resistance, and adhesion.

[0054] For the initial adhesive force of the bakelite board The initial adhesion of the organic gel to bakelite boards can be determined by the following method.

[0055] An organic gel, molded into a sheet and covered on both sides with PET film, was used as a test piece. The PET film on one side of the test piece was peeled off, and the peeled-off side was adhered to a bakelite board. The bakelite board was placed in a tensile testing machine, and based on JIS Z0237, at 23°C and 55% relative humidity, the load was measured when the test piece was peeled off at a speed of 300 mm / min along a 90° direction. The measured load (N / 20 mm) was taken as the initial adhesive force (F0) to the bakelite board. A TENSILON "RTE-1210" (manufactured by ORIENTEC) tensile testing machine is preferably used. Typically, the initial adhesive force to the bakelite board can be determined by the method described in the examples.

[0056] From the viewpoint of the persistence and adhesion of the adhesive force, the initial adhesive force for the bakelite board is preferably 1.0 N / 20 mm or more, more preferably 5 N / 20 mm or more, and even more preferably 10 N / 20 mm or more.

[0057] Adhesive retention rate of organic gel The adhesive retention rate of organic gels can be determined by the following methods.

[0058] An organic gel, molded into a sheet and covered on both sides with PET film, was used as a test piece. The PET film on one side of the test piece was peeled off, immersed in water for 1 hour, and allowed to stand. The test piece was then removed from the water, and surface moisture was removed. The peeled-off side of the test piece was adhered to a bakelite board. The bakelite board was placed in a tensile testing machine, and based on JIS Z 0237, at 23°C and 55% relative humidity, the load when the test piece was peeled off at a speed of 300 mm / min along a 90° direction was measured. The measured load (N / 20 mm) was taken as the adhesive force (F1) of the organic gel after immersion in water. The adhesive force retention rate (%) of the organic gel was obtained by dividing the adhesive force (F1) of the organic gel after immersion in water by the initial adhesive force (F0) to the bakelite board, and multiplying by 100 [Adhesive force retention rate (%) = F1 / F0 × 100]. Typically, the adhesive force retention rate of the organic gel can be determined by the method described in the examples.

[0059] From the viewpoint of water resistance, the adhesive strength retention rate of the organic gel is preferably 90% or more, more preferably 93% or more, and even more preferably 95% or more.

[0060] The shape of the organic gel of the present invention is not particularly limited, and it can be in the form of sheets, any three-dimensional shape, etc., but it is preferably in the form of sheets. The shape of the organic gel sheet can be set to any shape according to the purpose, such as roughly rectangular, roughly circular, etc., but is not limited to this.

[0061] The thickness of the organic gel can be adjusted according to its application and is not particularly limited. From the point of view of adhesion, it is preferred to be in the range of 100 μm to 1000 μm, and more preferably in the range of 300 μm to 600 μm.

[0062] Methods for manufacturing organic gels The organic gel of the present invention can be manufactured by the following method.

[0063] The process includes: firstly, mixing (meth)acrylates having an alicyclic hydrocarbon with a plasticizer to obtain a mixture. The mixture may further contain at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers, a crosslinking monomer, a polymerization initiator, and one or more additives (rust inhibitors, mildew inhibitors, antioxidants, defoamers, stabilizers, surfactants, colorants, thickeners, humectants, fragrances). The polymerization of (meth)acrylates is promoted by including a polymerization initiator in the mixture. These materials are as described above as components of the organic gel.

[0064] When mixing (meth)acrylates containing alicyclic hydrocarbons with plasticizers, these components can be mixed at once or mixed separately.

[0065] Next, the above mixture is injected into a container of the desired shape and allowed to solidify, thus forming the organic gel. In the case of forming a sheet, for example, the above mixture is dropped onto a membrane, further covering it, and then the mixture is spread evenly to a desired thickness and allowed to solidify, thus forming the organic gel.

[0066] There are no particular limitations on the curing method; any known method can be used. In the case of curing via polymerization irradiation using ultraviolet light, a cumulative ultraviolet irradiation dose of 1000 mJ / cm² is desired. 2 above.

[0067] Typically, organic gels are manufactured using the methods described in the examples.

[0068] According to the above method, an organic gel can be manufactured, which comprises a polymer matrix and a plasticizer. The water content is less than 1% by mass relative to the total amount of the organic gel. The organic gel contains (meth)acrylates having alicyclic hydrocarbons in their structure as polymerizable monomers constituting the polymer matrix. The plasticizer is a plasticizer selected from aliphatic hydrocarbons and fatty acid esters that is liquid or paste-like at 25°C. The organic gel has an initial adhesion force of 1.0 N / 20 mm or more to bakelite boards and retains an adhesion force of 90% or more after immersion in water for 1 hour.

[0069] Other components of organic gels Organogels can be designed such that their surfaces in contact with the outside are covered by a substrate composed of woven fabric, nonwoven fabric, or membrane, either on one side or multiple sides. Organogels can also have an intermediary substrate composed of woven or nonwoven fabric embedded within them. The substrate or intermediary substrate is related to the reinforcement of the organogel and the improvement of its shape retention during cutting.

[0070] Nonwoven and woven fabrics can be made from natural fibers such as cellulose, silk, and hemp, or synthetic fibers such as polyester, nylon, rayon, polyethylene, polypropylene, and polyurethane, or blends thereof. Adhesives may be used as needed. Membranes can be made from materials such as polyester, nylon, polyethylene, polypropylene, and polyurethane.

[0071] There are no particular limitations on the manufacturing method of nonwoven fabrics, and examples include dry bonding, wet bonding, spunbonding, meltblown bonding, air-laid bonding, chemical bonding, thermal bonding, needle punching, and hydroentangling. A manufacturing method appropriate to the weight per unit area and material is preferred, and to control the position of the intermediate substrate, it is preferable to have no uneven weight per unit area. Regarding weaving, plain weave, tricot, raschel, etc., are not particularly limited and can be appropriately selected.

[0072] There is no particular limitation on the weight per unit area of ​​woven or nonwoven fabrics; for example, it is preferably 10~40 g / m². 2 More preferably 10~28 g / m 2 . The thickness of the intermediate substrate is not particularly limited, but is preferably 50 to 1000 μm, more preferably 50 to 500 μm, and even more preferably 80 to 300 μm.

[0073] The organic gel of the present invention can also be used in combination with known materials. The organic gel of this invention possesses moderate elasticity and excellent water resistance, as well as superior adhesion and appearance. Therefore, it can be used in numerous fields such as medical, cosmetic, food, chemical, bioengineering, and sports-related applications. For example, it can be suitably used as an organic gel that adheres to the body, such as in monitoring machines for electrocardiogram measurement, medical electrodes in devices for treatment using low-frequency, medium-frequency, and high-frequency electrical stimulation, skin patches in devices for examination using ultrasound, counter plates for electrosurgical units, and adhesive materials for nail art.

[0074] The invention will be described in more detail using examples, but the invention is not limited to these examples. Example

[0075] 1. Manufacturing of organic gels (Example 1) First, relative to 100 parts by weight of 4-tert-butylcyclohexyl acrylate (trade name "TBCHA", manufactured by KJ Chemicals Co., Ltd.), 2.0 parts by weight of 2-hydroxy-2-methylphenylacetone (trade name "Omnirad 1173", manufactured by IGMresins BV) as a polymerization initiator was added, and the mixture was stirred until completely dissolved. Then, 66.6 parts by weight of liquid paraffin (trade name "Liquid Paraffin No. 380-S", manufactured by Sanko Chemical Industry Co., Ltd.) as a plasticizer was added to the resulting solution, and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Next, the obtained monomer complex liquid was droplet-added onto a silicone-coated PET film. Another silicone-coated PET film was then placed on top, thus spreading the liquid evenly and fixing it to a thickness of 300 μm. The mixture was then irradiated with a metal halide lamp at an energy of 3000 mJ / cm². 2 Ultraviolet light was used to create a sheet-like organic gel with a thickness of 300 μm.

[0076] (Example 2) When obtaining the monomer complex solution, 2.0 parts by weight of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by weight of 3,3,5-trimethylcyclohexyl acrylate (trade name "TMCHA", manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the mixture was stirred until completely dissolved. 66.6 parts by weight of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution, and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0077] (Example 3) When obtaining the monomer complex solution, 1.0 part by weight of polyalkylene glycol dimethacrylate (trade name "BLEMMER-PDE-400", manufactured by Nippon Oil Co., Ltd.) as a crosslinking monomer was added relative to 100 parts by weight of 4-tert-butylcyclohexyl acrylate. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0078] (Example 4) When obtaining the monomer complex liquid, 42.9 parts by weight of liquid paraffin No. 380-S as a plasticizer were added, and otherwise an organic gel was prepared by the same method as in Example 1.

[0079] (Example 5) When obtaining the monomer complex liquid, 100 parts by weight of liquid paraffin No. 380-S as a plasticizer were added, and otherwise an organic gel was prepared by the same method as in Example 1.

[0080] (Example 6) When obtaining the monomer complex solution, 2 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by mass of a mixture of 50 parts by mass of 4-tert-butylcyclohexyl acrylate and 50 parts by mass of n-octyl acrylate (trade name "NOAA", manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the mixture was stirred until completely dissolved. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0081] (Example 7) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by mass of a mixture of 75 parts by mass of 4-tert-butylcyclohexyl acrylate and 25 parts by mass of isodecyl acrylate (trade name "IDAA", manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the mixture was stirred until completely dissolved. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0082] (Example 8) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by mass of a mixture of 95 parts by mass of 4-tert-butylcyclohexyl acrylate and 5 parts by mass of N,N-diethylacrylamide (trade name "DEAA", manufactured by KJ Chemicals Co., Ltd.), and stirred until completely dissolved. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0083] (Example 9) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by mass of a mixture of 95 parts by mass of 4-tert-butylcyclohexyl acrylate and 5 parts by mass of N,N-dimethylacrylamide (trade name "DMAA", manufactured by KJ Chemicals Co., Ltd.), and stirred until completely dissolved. Otherwise, an organic gel was prepared by the same method as in Example 1.

[0084] (Example 10) When obtaining the monomer complex liquid, 66.6 parts by weight of isohexadecane (trade name "Permethyl 101A", manufactured by Nippon Koken Kogyo Co., Ltd.) as a plasticizer and 2.0 parts by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0085] (Example 11) When obtaining the monomer complex liquid, 66.6 parts by weight of squalane (trade name "OLIVE SQUALANE", manufactured by Advanced Alcohols Industry Co., Ltd.) as a plasticizer and 2.0 parts by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0086] (Example 12) When obtaining the monomer complex liquid, 66.6 parts by weight of hydrogenated polyisobutylene (trade name "PARLEAM 6", manufactured by Nippon Oil Co., Ltd.) as a plasticizer and 2 parts by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0087] (Example 13) When obtaining the monomer complex, 66.6 parts by weight of hydrogenated polydecene (trade name "SILKFLO 366", manufactured by INEOS Oligomers USA LLC) as a plasticizer and 2 parts by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0088] (Example 14) When obtaining the monomer complex liquid, 66.6 parts by weight of castor oil (trade name "Marutoku A", manufactured by Ito Oil Co., Ltd.) as a plasticizer and 2.0 parts by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0089] (Example 15) When obtaining the monomer complex, 66.6 parts by weight of glyceryl triisostearate (trade name "Sunoil O-183", manufactured by Taiyo Chemical Co., Ltd.) as a plasticizer were added, and otherwise an organic gel was manufactured by the same method as in Example 1.

[0090] (Example 16) When obtaining the monomer complex liquid, 50 parts by weight of liquid paraffin No. 380-S as a plasticizer and 16.6 parts by weight of silicone oil (trade name "KF-96A-6CS", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added, and an organic gel was manufactured by the same method as in Example 1.

[0091] (Example 17) When obtaining the monomer complex liquid, 58.3 parts by weight of liquid paraffin No. 380-S as a plasticizer, 8.3 parts by weight of shea butter (trade name "SHEA BUTTER RF", manufactured by Advanced Alcohols Industry Co., Ltd.) as a humectant, and 1.0 part by weight of polyalkylene glycol dimethacrylate as a crosslinking monomer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0092] (Comparative Example 1) When obtaining the monomer complex solution, 66.6 parts by weight of polyoxypropylene diglyceride (trade name "SC-P1000", manufactured by Sakamoto Pharmaceutical Co., Ltd.) as a plasticizer were added, and otherwise an organic gel was manufactured by the same method as in Example 1.

[0093] (Comparative Example 2) When obtaining the monomer complex liquid, 66.6 parts by weight of polyoxyethylene methyl glucoside (trade name "MG-10E", manufactured by Nippon Oil Co., Ltd.) as a plasticizer were added, and otherwise an organic gel was manufactured by the same method as in Example 1.

[0094] (Comparative Example 3) When obtaining the monomer complex solution, 2 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator were added to 100 parts by mass of 1,4-cyclohexanediethanol monoacrylate (trade name "CHDMMA", manufactured by Nippon Chemical Co., Ltd.), and the mixture was stirred until completely dissolved. 66.6 parts by mass of SC-P1000 as a plasticizer were added to the resulting solution, and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0095] (Comparative Example 4) When obtaining the monomer complex liquid, 66.6 parts by weight of castor oil (trade name "castor hardening oil A", manufactured by Ito Oil Co., Ltd.) which is solid at 25°C was added as a plasticizer, and an organic gel was manufactured by the same method as in Example 1.

[0096] (Comparative Example 5) When obtaining the monomer complex liquid, 66.6 parts by weight of alkyl organosilicon (trade name "Microcare Silicone W3045", manufactured by THOR JAPAN Co., Ltd.) which is solid at 25°C and acts as a plasticizer were added. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0097] (Comparative Example 6) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator and 2 parts by mass of BLEMMER-PDE-400 as a crosslinking monomer were added relative to 100 parts by mass of n-octyl acrylate. The mixture was stirred until completely dissolved. 66.6 parts by mass of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was prepared by the same method as in Example 1.

[0098] (Comparative Example 7) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator and 2 parts by mass of polyalkylene glycol dimethacrylate as a crosslinking monomer were added relative to 100 parts by mass of isodecanyl acrylate. The mixture was stirred until completely dissolved. 66.6 parts by mass of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was prepared by the same method as in Example 1.

[0099] (Comparative Example 8) When obtaining the monomer complex solution, 2 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator and 2.0 parts by mass of polyalkylene glycol dimethacrylate as a crosslinking monomer were added to 100 parts by mass of 2-ethylhexyl acrylate (trade name "2-EHA", manufactured by Mitsubishi Chemical Corporation). The mixture was stirred until completely dissolved. 66.6 parts by mass of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0100] (Comparative Example 9) When obtaining the monomer complex solution, 2.0 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator and 2 parts by mass of polyalkylene glycol dimethacrylate as a crosslinking monomer were added relative to 100 parts by mass of butyl acrylate (trade name "BA", manufactured by Mitsubishi Chemical Corporation). The mixture was stirred until completely dissolved. 66.6 parts by mass of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0101] (Comparative Example 10) When obtaining the monomer complex solution, 2 parts by mass of 2-hydroxy-2-methylphenylacetone as a polymerization initiator and 2.0 parts by mass of polyalkylene glycol dimethacrylate as a crosslinking monomer were added relative to 100 parts by mass of lauryl acrylate (trade name "LA", manufactured by Osaka Organic Chemical Industry Co., Ltd.). The mixture was stirred until completely dissolved. 66.6 parts by mass of liquid paraffin No. 380-S as a plasticizer were added to the resulting solution and the mixture was stirred to obtain a colorless and transparent monomer complex solution. Otherwise, an organic gel was manufactured by the same method as in Example 1.

[0102] 2. Measurement or evaluation methods and evaluation criteria (1) Evaluation of whether gel can form The following criteria were used to evaluate whether gels could be formed in the compositions obtained in Examples 1-17 and Comparative Examples 1-10 by visual observation. Acceptable: Solids with overall shape retention, no cracks or damage were observed when bent 180°. Unacceptable: Liquids or pastes that lack overall shape retention, or even solids with overall shape retention, showed cracking or damage when bent at 180°. The organic gels of Examples 1-17, Comparative Examples 3, 6-8 and 10, which were qualified to form gels, were further tested and evaluated as follows (2) to (7).

[0103] (2) Evaluation of the appearance of the gel The appearance of each organic gel obtained in Examples 1-17, Comparative Examples 3, 6-8 and 10 was observed by the naked eye and evaluated based on the following criteria. Good: The gel is transparent. Undesirable: The gel may be cloudy or have plasticizer exudation.

[0104] (3) Determination of the moisture content of the gel Take 100 mg of each organic gel obtained in Examples 1-17, Comparative Examples 3, 6-8 and 10, add it to a vial, seal it with an aluminum cap, and use it as a test sample. The test sample was placed in a moisture vaporization apparatus (VA-230, Mitsubishi Chemical Analytech, Ltd.). The vial was then heated to 125°C to vaporize the moisture in the sample, and the vaporized moisture content was measured using a moisture analyzer (KF-200, Mitsubishi Chemical Analytech, Ltd.). The measured value (mg) was divided by the mass of the organic gel (100 mg) and multiplied by 100 to obtain the moisture content (%) of the organic gel.

[0105] (4) Determination of initial adhesive force The organic gels obtained in Examples 1-17, Comparative Examples 3, 6-8 and 10 were cut into pieces with a width of 20 mm and a length of 120 mm to serve as test pieces. Peel off the PET film from one side of the test piece, and then attach the peeled side to a bakelite board and mount it on a TENSILON (ORIENTEC "RTE-1210"). Then, according to JIS Z 0237, in an environment of 23°C and 55% relative humidity, measure the load when peeling the test piece at a speed of 300 mm / min along a 90° direction. The measured load value (N / 20 mm) is taken as the initial adhesive force of the organic gel.

[0106] (5) Determination of adhesive strength after immersion in water The organic gels obtained in Examples 1-17, Comparative Examples 3, 6-8 and 10 were cut into pieces with a width of 20 mm and a length of 120 mm to serve as test pieces. Peel off the PET film from one side of the test piece, immerse it in water for 1 hour, and let it stand. Then, remove the test piece from the water and remove the surface moisture. Next, attach the peeled-off side of the test piece to a bakelite board. According to JIS Z 0237, in an environment of 23°C and 55% relative humidity, measure the load when peeling the test piece at a speed of 300 mm / min along a 90° direction. The measured load value (N / 20 mm) is taken as the adhesive force of the organic gel after immersion in water.

[0107] (6) Calculation of Adhesive Strength Retention Rate The adhesion retention rate was calculated using the following calculations. Adhesion retention rate (%) = F1 / F0 × 100 F0: Initial adhesive force of the organic gel. F1: Adhesive strength of organic gel after immersion in water.

[0108] (7) Evaluation of long-term adhesion The organic gels obtained in Examples 1-17, Comparative Examples 3, 6-8, and 10 were cut into circles with a diameter of 3 cm. One side of the PET film was peeled off and adhered to a nonwoven fabric (trade name "Sontara," Nissei Co., Ltd.) used as the surface material to obtain an adhesion sample. The long-term adhesion was evaluated by peeling off the other PET film of the adhesion sample and applying it to human skin (chest). A: It can be worn for more than a week. B: The sample can be applied for more than one day, but if it is less than one week, the sample will fall off the skin. C: The attached sample detaches from the skin in less than one day (less than 24 hours). The results of the evaluation and measurement of (1) to (7) above are shown in Table 1 and Table 2.

[0109] [Table 1]

[0110] [Table 2] .

Claims

1. An organic gel comprising a polymer matrix and a plasticizer, The moisture content relative to the total amount of the organic gel is less than 1.0% by mass. The organic gel contains (meth)acrylates having alicyclic hydrocarbons in their structure as polymerizable monomers constituting the polymer matrix. The plasticizer is a plasticizer containing at least one selected from aliphatic hydrocarbons, fatty acid esters, and silicone oils, and is liquid or paste-like at 25°C. The organic gel has an initial adhesion force of 1.0 N / 20 mm or more to the bakelite board, and retains more than 90% of the adhesion force after immersion in water for 1 hour.

2. The organic gel according to claim 1, wherein, The (meth)acrylate having an alicyclic hydrocarbon in its structure includes 4-tert-butylcyclohexyl acrylate.

3. The organic gel according to claim 1, further comprising at least one monomer selected from (meth)acrylamide monomers and (meth)acrylate monomers as a polymerizable monomer constituting the polymer matrix.

4. The organic gel according to claim 1, wherein, The amount of the (meth)acrylate having an alicyclic hydrocarbon in the structure is 30% by mass or more relative to the total amount of the polymer matrix.

5. The organic gel according to claim 1, wherein, The content of the plasticizer is 10 to 60% by mass relative to the total amount of organic gel.

6. The organic gel according to any one of claims 1 to 5, wherein the thickness is in the range of 100 μm to 1000 μm.

Images