Silicone adhesive-based ultra-thin type patch for outdoor activities

Abstract

This specification relates to an ultra-thin outdoor activity patch based on a silicone adhesive. According to one aspect of the invention, an ultra-thin UV-blocking patch can be provided that has excellent UV-blocking effects without compromising transparency and physical properties, and an ultra-thin UV-blocking patch can be provided in which the release layer can be easily removed and skin adhesion is maintained even after long-term storage.

Description

Technology Field

[0001] This specification relates to an ultra-thin outdoor activity patch based on a silicone adhesive. Background Technology

[0002] Ultraviolet (UV) rays contained in sunlight are known to be a major cause of various skin diseases, such as erythema, edema, photoaging, and skin cancer, when they reach the human skin. Accordingly, social awareness of the importance of effectively protecting the skin from UV rays is increasing, and the need for the development of related technologies is also continuously being emphasized.

[0003] Generally, UV protection is achieved through physical barriers using clothing or hats, or by applying cosmetics containing UV-blocking ingredients. UV-blocking cosmetics are classified into physical methods, where inorganic pigments scatter and reflect UV rays, and chemical methods, where organic compounds absorb UV rays and convert them into thermal energy. However, liquid or solid cosmetics have limitations in that they are easily washed away by sweat during prolonged outdoor activities, such as golf or hiking, which reduces the duration of their protective effect. Furthermore, inconvenience in use has been pointed out as a problem, such as causing pain if the sunscreen gets into the eyes along with sweat.

[0004] Furthermore, existing outdoor activity patches have the problem of becoming significantly thick due to the difficulty of applying adhesive to thin films. As a result, they have been less preferred by consumers who prioritize aesthetics.

[0005] To address these issues, there is a need to develop UV protection patches for outdoor activities that possess various functions without sacrificing aesthetics. Prior art literature

[0006] Republic of Korea Registered Patent No. 10-1696275 (2017.01.09.) The problem to be solved

[0007] The present specification aims to provide an ultra-thin UV blocking patch that has excellent UV blocking effect without compromising transparency and physical properties, and an ultra-thin UV blocking patch that is very thin while maintaining easy removal of the release layer and skin adhesion. means of solving the problem

[0008] To solve the above problem, the present specification provides a carrier film layer released with fluorine or silicone;

[0009] A transparent outer film layer comprising polyurethane laminated on the carrier film layer;

[0010] An adhesive layer laminated on the above transparent outer film layer; and

[0011] A release liner laminated on the adhesive layer to protect the adhesive strength of the adhesive layer and removable according to the user's intention;

[0012] As a skin protection patch for outdoor activities comprising,

[0013] The above transparent outer film layer is polyurethane, and

[0014] A skin protection patch for outdoor activities is provided, which contains a triazine-based UV absorber. Effects of the invention

[0015] A skin protection patch for outdoor activities according to one aspect of the present invention effectively blocks ultraviolet rays in both UVA and UVB regions without the need for a separate sunscreen to be applied to the skin, maintains excellent skin adhesion despite its thin thickness, and allows for convenient use for a long period of time as the release liner is easy to remove even when used after long-term storage. Brief explanation of the drawing

[0016] FIG. 1 briefly illustrates a corona discharge treatment according to one aspect of the present invention. Specific details for implementing the invention

[0017] The present invention may be subject to various modifications, and therefore the scope of the patent application is not limited or restricted by the embodiments, comparative examples, and experimental examples. It should be understood that all modifications, equivalents, and substitutions to the embodiments, comparative examples, and experimental examples are included within the scope of the patent application.

[0018] Specific structural or functional descriptions of the present invention are disclosed merely for illustrative purposes and may be modified and implemented in various forms. Accordingly, the present invention is not limited to specific disclosed forms, and the scope of this specification includes modifications, equivalents, or substitutions that fall within the technical concept.

[0019] The terms used in this specification are for illustrative purposes only and should not be interpreted as being limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. Terms such as “contain,” “include,” or “have” in this specification are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in this specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0020] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the embodiments pertain. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this specification.

[0021] The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments, comparative examples, and experimental examples described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments, comparative examples, and experimental examples disclosed below, but may be implemented in various different forms. These embodiments, comparative examples, and experimental examples are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims.

[0022] In the embodiments, comparative examples, experimental examples, etc. of the present invention, all terms used herein, including technical or scientific terms, unless otherwise defined, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in the embodiments of the present invention. Furthermore, in interpreting the components, they are interpreted to include a margin of error even without separate explicit description.

[0023] The features of each of the various embodiments, comparative examples, and experimental examples of the present invention may be combined or combined with one another, either partially or wholly, and as will be fully understood by those skilled in the art, various technical interlocking and operation are possible, and each embodiment, comparative example, and experimental example may be implemented independently of one another or may be implemented together in an interrelationship.

[0024] This specification

[0025] A carrier film layer released with fluorine or silicone;

[0026] A transparent outer film layer comprising polyurethane laminated on the carrier film layer;

[0027] An adhesive layer laminated on the above transparent outer film layer; and

[0028] A release liner laminated on the adhesive layer to protect the adhesive strength of the adhesive layer and removable according to the user's intention;

[0029] As a skin protection patch for outdoor activities comprising,

[0030] The above transparent outer film layer

[0031] Polyurethane; and

[0032] Triazine-based UV absorber;

[0033] It may be related to a skin protection patch for outdoor activities that includes.

[0034] In one aspect, the carrier film layer released with fluorine or silicone may include a substrate layer and a coating layer.

[0035] In another aspect, the transparent outer film layer may further comprise one or more selected from the group consisting of ethyl acetate, butyl acetate, and methyl ethyl ketone (MEK).

[0036] In another aspect, the substrate layer may comprise at least one of polyethylene resin, polyethylene terephthalate resin, polyetheretherketone resin, polyimide resin, polypropylene resin, stretched polypropylene resin, cellulose, and polyvinyl chloride resin, but is not limited thereto.

[0037] In another aspect, the thickness of the carrier film layer released with fluorine or silicone may be 0.01 mm or more and 0.1 mm or less. Meanwhile, the coating layer on the surface of the carrier film layer released with fluorine or silicone may be 5 μm or more and 50 μm or less. If the thickness of the substrate layer deviates from the above numerical range, defects may occur in the durability of the carrier film layer released with silicone. In addition, if the thickness of the coating layer deviates from the above range, the carrier film and the transparent outer film may separate too easily or be difficult to separate, resulting in the loss of function as a transparent patch.

[0038] In one aspect, the coating layer may comprise a cured product of a silicon-based coating composition. Here, the silicon-based coating composition may comprise a silicon-based resin, a silicon-based crosslinking agent, a metal catalyst, and a silicon-based compound represented by the following chemical formula 1.

[0039] [Chemical Formula 1]

[0040]

[0041] In the above chemical formula 1, m is an integer from 600 to 1000.

[0042] The above silicone-based resin may be vinyl-terminated polydimethylsiloxane.

[0043] The above silicone-based crosslinking agent may be at least one selected from the group consisting of dimethylhydrogensiloxy group end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-blocked poly(methylhydrogensiloxane), poly(hydrogensilsesquioxane), and methylhydrogensiloxane, but is not necessarily limited thereto.

[0044] The above metal catalyst may include a platinum-based catalyst. The platinum-based catalyst may include at least one selected from the group consisting of particulate platinum, particulate platinum adsorbed on a carbon powder support, chloroplatinic acid, alcohol-modified chloroplatinic acid, and olefin complexes of chloroplatinic acid, but is not necessarily limited thereto.

[0045] The above silicone-based coating composition may further include at least one of a release agent, silica particles, and a photoinitiator.

[0046] The above silicone-based coating composition can be cured through photocuring or thermal curing. Specifically, the silicone-based coating composition can be thermally cured, and the thermal curing of the silicone-based coating composition can be performed at a temperature of 100°C or higher and 180°C or lower for a time of 30 seconds or more and 180 seconds or less. When the curing temperature and curing time of the silicone-based coating composition satisfy the above numerical ranges, the silicone-based coating composition can be stably cured to improve the durability of the cured product.

[0047] The thickness of the coating layer may be 10㎛ or more and within 50㎛.

[0048] The carrier film layer treated with fluorine or silicone can reduce the crosslinking density of the coating layer to maximize the flexibility of the coating layer and thereby reduce the release peel force, thus preventing the problem of deterioration of the adhesive properties due to silicone transfer and the occurrence of blocking problems caused by a thick coating layer.

[0049] The thickness of the carrier film layer may be 0.01 to 0.1 mm.

[0051] A transparent outer film layer containing the above-mentioned polyurethane can be formed by applying a polyurethane dispersion to the carrier film layer. The polyurethane dispersion can be prepared from a nonionic polyurethane prepolymer. The nonionic prepolymer of the present invention can be prepared using an aliphatic or aromatic diisocyanate. Preferably, the diisocyanate may be an aromatic diisocyanate selected from the group consisting of MDI, TDI, and mixtures thereof.

[0052] The above-mentioned nonionic prepolymer may be prepared from a formulation containing an active hydrogen-containing material. The active hydrogen-containing material may be a mixture of diols.

[0053] The above nonionic prepolymer may be dispersed in water in the presence of a surfactant. Here, the surfactant is an anionic surfactant and may be at least one selected from the group consisting of sodium dodecyl benzene sulfonate, dodecyl sodium sulfonate, sodium dodecyl diphenyl oxide disulfonate, sodium n-decyl diphenyl oxide disulfonate, isopropylamine dodecylbenzene sulfonate, or sodium hexyl diphenyl oxide disulfonate.

[0054] The above polyurethane dispersion can be diluted before final use, and can be used by diluting it so that the polyurethane solid content is 5 to 20% based on the polyurethane dispersion. When the solid content concentration of the polyurethane dispersion has the above numerical range, it is possible to realize an ultra-thin skin protection patch for outdoor activities with a thickness thinner than conventional patches.

[0055] In one aspect, the thickness of the transparent outer film layer may be 1 μm or more to less than 5 μm. Preferably, it may be 0.001 mm to 0.0049 mm.

[0056] In another aspect, the transparent outer film layer may comprise 0.5 to 10 parts by weight of a triazine-based ultraviolet absorber.

[0057] As one embodiment, the triazine-based UV absorber may comprise a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-didecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tinuvin® 400) and 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine (Tinuvin® 477).

[0058] As another embodiment, the triazine-based ultraviolet absorber may comprise a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-didecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine in a weight ratio of 1:1 to 1:5.

[0059] As another embodiment, the triazine-based UV absorber may include bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb® S).

[0060] As an example, the above triazine-based ultraviolet absorber may comprise 1 to 3.1 parts by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine based on 100 parts by weight of the above polyurethane.

[0061] As another example, the triazine-based UV absorber may comprise 0.7 to 1.6 parts by weight of 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylidenoxy]phenyl]-s-triazine (Tinuvin 477) when there are 2 parts by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine based on 100 parts by weight of the polyurethane. Meanwhile, the triazine-based UV absorber may comprise 1.6 to 2.3 parts by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine when there is 1 part by weight of 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylidenoxy]phenyl]-s-triazine (Tinuvin 477) based on 100 parts by weight of the polyurethane.

[0062] As another example, the thickness of the outer film layer containing the polyurethane may be 5 to 10 μm.

[0063] As another example, one side of the transparent outer film layer may have a primer coating or polar groups introduced to improve adhesion with the adhesive layer. Preferably, the introduction of polar groups may be achieved by corona discharge treatment.

[0064] Meanwhile, a primer capable of improving adhesion between the outer film layer and the adhesive layer laminated on the outer film layer may be applied to one side of the transparent outer film layer containing the polyurethane. The primer may include a linear polyorganosiloxane containing two or more alkenyl groups per molecule represented by the following chemical formula 2, a polyorganohydrogensiloxane containing hydrogen groups in the molecular side chain, reinforcing silica, an addition reaction catalyst, and an adhesion promoter comprising 1-allyl-3,5-diglycidyl isocyanurate.

[0065] [Chemical Formula 2]

[0066] R-Si(CH3)2O(R 1 2SiO) n Si(CH3)2-R

[0067] In the above chemical formula 2, R is a vinyl group, R 1 represents methyl or vinyl, and n is an integer from 50 to 250.

[0068] The above alkenyl group may be at least one selected from the group consisting of vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and heptenyl group, but is not necessarily limited thereto.

[0069] The alkenyl group may be contained in an amount of 0.001 to 5 mmol per g of polyorganosiloxane, and preferably in an amount of 0.01 to 3 mmol / g.

[0070] The above polyorganohydrogensiloxane may be represented by the following chemical formula 3.

[0071] [Chemical Formula 3]

[0072] R 2 -Si(CH3)2O(R 2 HSiO) x (R 2 SiO) y Si(CH3)2-R 2

[0073] In the above chemical formula 3, each R 2 is independently methyl, ethyl, butyl, or phenyl, and x and y are each independently integers from 10 to 100.

[0074] The hydrogen groups contained in the molecular side chains may be contained in an amount of 0.1 to 20 mmol per g of polyorganohydrogensiloxane.

[0075] The reinforcing silica mentioned above is not particularly limited as long as it is composed mainly of SiO2, and preferably fumed silica, precipitated silica, diatomite, crushed quartz, fused quartz, etc., can be used alone or in a mixture of two or more types.

[0076] A platinum compound may be used as the catalyst for the above addition reaction, and in this case, the platinum in the platinum compound acts as a catalyst to crosslink polyorganosiloxanes containing alkenyl groups and polyorganohydrogensiloxanes.

[0077] The above adhesion promoter may be used by using 1-allyl-3,5-diglycidyl isocyanurate alone or by mixing 1-allyl-3,5-diglycidyl isocyanurate with adhesion promoter components (organosilicon compounds, organic titanium compounds, etc.) that are typically added to silicone rubber. The above adhesion promoter can provide adhesion to the outer film layer and adhesion to the adhesive layer.

[0078] The above adhesive layer may include polydimethylsiloxane having vinyl groups at both ends, hydride-terminated polydimethylsiloxane, trimethylsiloxysilicate, 1-ethylcyclohexanol, corticosteroid, polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE).

[0079] Specifically, the adhesive layer may comprise 30 to 40 parts by weight of polydimethylsiloxane having vinyl groups at both ends, 1 to 2 parts by weight of hydride-terminated polydimethylsiloxane, 40 to 50 parts by weight of trimethylsiloxysilicate, 0.05 to 0.2 parts by weight of 1-ethylcyclohexanol, 5 to 15 parts by weight of corticosteroid, 1 to 3 parts by weight of polyvinylidene fluoride (PVDF), and 5 to 10 parts by weight of polytetrafluoroethylene (PTFE).

[0080] The polydimethylsiloxane having the above vinyl groups at both ends provides mechanical flexibility to the adhesive layer and may be represented by the following chemical formula 4.

[0081] [Chemical Formula 4]

[0082] Vi(CH3)2SiO-[(CH3)2SiO] n -Si(CH3)2Vi

[0083] Here, "Vi" refers to a vinyl group (-CH=CH2), and n refers to the average number of dimethylsiloxane units, which is the degree of polymerization (DP) for polydimethylsiloxane having vinyl groups at both ends. Typically, n can have a value of 25 to 200 or less, preferably 40 to 170 or less, more preferably 70 or more and 130 or less.

[0084] The polydimethylsiloxane having vinyl groups at both ends may have a silanol content of 3 to 4, preferably 3.2 to 3.8 parts by weight, and more preferably 3.5 parts by weight, based on 100 parts by weight of the polydimethylsiloxane having vinyl groups at both ends.

[0085] The above hydride-terminated polydimethylsiloxane functions as a crosslinking agent and may be represented by the following chemical formula 5.

[0086] [Chemical Formula 5]

[0087] H(CH3)2SiO-[(CH3)2)SiO)] m -Si(CH3)2H

[0088] Here, the subscript m can have a value of 10 to 100, preferably 20 to 80, more preferably 40 to 60.

[0089] The above trimethylsiloxysilicate can play an auxiliary role in increasing the adhesive strength of the adhesive layer by being applied together with other compositions of the adhesive layer.

[0090] The above 1-ethylcyclohexanol functions as a retardant to control the curing speed, thereby enabling curing to occur within a desired time.

[0091] The above-mentioned corticosteroid can improve the adhesive strength of the adhesive by being applied to the adhesive layer together with polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). Accordingly, even if the skin protection patch for outdoor activities according to the present invention is implemented with a thin thickness, it is possible to prevent the phenomenon in which the outer film layer and the adhesive layer separate due to low adhesive strength of the adhesive layer when the patch is detached from the skin after being attached. In addition, by applying the above-mentioned corticosteroid together with polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), the adhesive strength of the adhesive layer to the skin is also improved, so that the adhesive strength of the skin protection patch for outdoor activities can be maintained even when in contact with sweat or other moisture.

[0092] As an example, one side of the transparent outer film layer may be corona discharge treated to improve adhesion with the adhesive layer.

[0093] When corona discharge treatment is applied to the surface of a transparent polyurethane outer film layer, the surface energy increases and polar functional groups are introduced, thereby enhancing wettability, chemical bonding, and physical bonding with non-polar adhesives such as silicone adhesives. Polyurethane generally consists of a repeating urethane bond structure (-[R-NH-CO-O-R']-n), where R and R' are hydrocarbon chains of polyols and isocyanates. Furthermore, the surface mostly contains non-polar alkyl groups, ether groups, carbonyl groups, etc. Since the surface of the polyurethane layer has relatively low surface energy, silicone-based adhesives do not wet well. Corona discharge treatment is applied to the polyurethane to address this issue. Upon corona discharge treatment, methylene, ether groups, carbonyl groups, etc., on the surface of the polyurethane layer react with active species generated in the discharge region to produce polar functional groups. The polar functional groups generated at this time include hydroxyl groups (-OH), carbonyl groups, carboxylic acid groups (-COOH), peroxide groups (-O-OH), and epoxy groups (-COC-). These functional groups cause physical / chemical interactions (e.g., hydrogen bonding) with the silicone adhesive layer. Since the silicone adhesive layer is typically very non-polar and has low surface energy, the inventor of the present invention conceived of corona discharge treatment as a measure to improve wettability and adhesion between the polyurethane layer and the silicone adhesive layer.

[0094] As another example, the adhesive layer may be a silicone-based adhesive layer with enhanced adhesion.

[0095] As another example, the above-mentioned release layer may have one side having an embossed structure.

[0096] In one aspect, the release layer may have one side having an embossed structure, wherein one side of the embossed structure may be treated with fluorine or silicone for release.

[0097] In another aspect, when applying a diluted polyurethane to one side of the silicone-released carrier film layer, one or more solvents selected from the group consisting of ethyl acetate, benzene, butyl acetate, toluene, xylene, methyl ethyl ketone (MEK), and acetone may be used.

[0098] For example, the thickness of the polyurethane outer film layer may be 1.1㎛ or more to less than 5㎛. If it is 5㎛ or more, it becomes cloudy and transparency decreases, and when attached to the skin, it causes a foreign sensation, which significantly impairs the value of the patch. If it is less than 1.1㎛, the UV blocking effect is significantly reduced and defects occur in physical properties such as the elasticity characteristic of polyurethane, so it cannot be used as a skin patch.

[0099] As another example, the thickness of the adhesive layer or adhesive layer formed by applying an adhesive composition may be 0.01 to 0.08 mm. Preferably, it may be 0.02 mm. If the adhesive layer is formed to be less than 0.01 mm, the adhesive strength is significantly reduced, making adhesion impossible; if it exceeds 0.08 mm, the adhesive layer becomes excessively thick, leading to problems such as reduced transparency, making it difficult to use as a skin patch. In the case of a silicone adhesive layer, it must be thicker than a certain thickness to achieve adhesive strength; however, if it becomes too thick, various cosmetics or skin products may accumulate or clump together on the patch when it is attached to the skin, causing an aesthetic issue. In one aspect, the present invention is said to have a technical feature of maintaining ultra-thinness while achieving adhesive strength of the silicone adhesive layer.

[0100] When forming the above release layer, the material of the release layer may be one or more selected from the group consisting of polyethylene, polypropylene, PET, polystyrene, PVC, and polyamide.

[0101] For example, the above embossing structure may be implemented by interlocking and rotating a male roller and a female roller having concave and convex surfaces and passing the release paper between them, but a method using only one of the male roller or the female roller may also be applicable.

[0103] Hereinafter, the composition of the present invention and the resulting effects are to be explained in more detail through specific embodiments, comparative examples, and experimental examples. However, these embodiments, comparative examples, and experimental examples are intended to explain the present invention more specifically, and the scope of the invention is not limited to these examples.

[0105] [Example 1]

[0106] First, a carrier film layer released with silicone was prepared. A silicone-based coating composition was prepared comprising 10 parts by weight of vinyl-terminated polydimethylsiloxane (Shin-Etsu Silicon Co. / KS-847H) having a weight-average molecular weight of 300,000 to 400,000 g / mol and a polydispersity index of 1.8 to 2.2, 1 part by weight of a silicone-based crosslinking agent (Shin-Etsu Silicon Co. / X-92-122), 3 parts by weight of a platinum-based catalyst (Shin-Etsu Silicon Co. / PL-50T), and 10 parts by weight of a silicone-based compound (MCR-V41), based on 100 parts by weight of tetrahydrofuran (THF). Subsequently, the prepared silicone-based coating composition was applied at 2.5 g / m² using a Meyerbar No. 8 on a 75 μm thick polyethylene terephthalate (PET, MCC / T10075S) or polyethylene (Sigma-Aldrich) substrate layer. 2 It was applied to a thickness of 0.05 mm. Subsequently, the silicone-based coating composition applied on the substrate was dried and cured at 130°C for 1 minute, and then aged at 50°C for 24 hours to produce a silicone-release carrier film (thickness 0.05 mm).

[0107] A transparent outer film was formed on one side of the carrier film layer released with the above silicone. Specifically, a polyurethane dispersion diluted with one or more selected from ethyl acetate, butyl acetate, and methyl ethyl ketone (MEK) (prepared from a nonionic prepolymer prepared using TDI among diisocyanates) was applied to one side of the carrier film layer to form a transparent outer film with a thickness of 0.003 mm. Here, when diluting the polyurethane, TINUVIN ® 400 and TINUVIN ® 477 was homogeneously mixed at 1.5 parts by weight and 2.5 parts by weight, respectively, relative to 100 parts by weight of polyurethane solids. At this time, the polyurethane was diluted so that the solid content concentration was 13% to 15%.

[0108] Next, a primer composition was applied onto an outer film. The primer composition contained 100 parts by weight of divinylpolydimethylsiloxane (viscosity at 25°C 10,000 mPa / s, vinyl group content 0.05 mmol / g), 13.9 parts by weight of polymethylhydrogensiloxane (Si-H group content 7.3 mmol / g), 32 parts by weight of fumed silica (QS-30, manufactured by Tokuyama Corporation), 0.13 parts by weight of a platinum compound (platinum-divinyltetramethyldisiloxane complex), an adhesion promoter (MA-DGIC, manufactured by Shikoku Corporation), 0.08 parts by weight of 1-ethynyl-1-cyclohexanol, 8 parts by weight of hexamethyldisilazane, and 2.3 parts by weight of purified water.

[0109] Subsequently, a silicone adhesive composition was applied onto an outer film coated with a primer. The adhesive composition is a polydimethylsiloxane (Vi(CH3)2SiO-[(CH3)2SiO] having vinyl groups at both ends. n -Si(CH3)2Vi, n is 80) 35 parts by weight, hydride-terminated polydimethylsiloxane (H(CH3)2SiO-[(CH3)2)SiO)] m-Si(CH3)2H, m is 50) 1 part by weight, trimethylsiloxysilicate 45 parts by weight, 1-ethylcyclohexanol 0.1 parts by weight, corticosteroid 10 parts by weight, polyvinylidene fluoride (PVDF) 1 part by weight, and polytetrafluoroethylene (PTFE) 5 parts by weight were mixed to prepare the adhesive composition. The thickness of the adhesive layer or adhesive layer formed by applying the adhesive composition was 0.02 mm.

[0110] Finally, a release layer (0.1 mm) made of polyethylene was formed on the adhesive layer to manufacture a skin protection patch for outdoor activities.

[0112] [Example 2]

[0113] Perform as in Example 1 above, provided that when diluting the polyurethane in the step of forming the polyurethane outer layer, TINUVIN ® 400 and TINUVIN ® TinoSorb instead of 477 ® S was made to be 2.0 parts by weight per 100 parts by weight of polyurethane solids.

[0115] [Example 3]

[0116] Perform as in Example 1 above, provided that when diluting the polyurethane in the step of forming the polyurethane outer layer, TINUVIN ® 400 and TINUVIN ® TinoSorb instead of 477 ® S and TINUVIN ® 477 was made so that it was 2.0 parts by weight and 1.0 parts by weight, respectively, relative to 100 parts by weight of polyurethane solid content.

[0118] [Example 4]

[0119] A carrier film layer released with fluorine was prepared. 2.85 g of methyl methacrylate (MMA, Samcheon Chemical, 99%), 0.15 g of 3-methacryloylpropyl trimethoxysilane (SZ-6030, Dow Corning), 0.02 g of 2,2'-azobis(4-methoxy-2,4-dimethyl vareronitrile) (V-70, Wako Pure Chemicals), and 12 g of isophorone (Sigma-Aldrich) were added to a 4-neck reactor and polymerized at 60°C for 6 hours to prepare a polymer binder. 5 g of PVDF (Alfa Aesar) as a fluorine-based polymer, 0.8 g of the above polymer binder, and 28 g of the organic solvent isophorone (Sigma-Aldrich) were mixed to prepare a fluorine-based coating composition with a solid content of 16 wt%. Subsequently, 2.5 g / m² of the prepared fluorine-based coating composition was applied to a 75 μm thick polyethylene terephthalate (PET, MCC / T10075S) or polyethylene (Sigma-Aldrich) substrate layer heated to 120°C. 2 A bar coating was applied to achieve a thickness of 0.05 mm. Afterward, the film was dried and cured for 10 minutes, and then aged at room temperature for 24 hours to produce a fluorine-release carrier film (thickness 0.05 mm).

[0120] A skin protection patch for outdoor activities was manufactured by following the subsequent procedure as in Example 1.

[0122] [Example 5]

[0123] In the above Example 1, corona discharge treatment was performed instead of the process of applying a primer composition onto the polyurethane outer film. The treatment was performed using a corona treatment device (15kW, Songwon Tech Co., Ltd., KR), and the specific conditions are as follows.

[0124] Reaction temperature and pressure: Room temperature, atmospheric pressure

[0125] Reacting gas: Air or Air + Argon (Ar)

[0126] Discharge voltage and frequency: 15 ~ 30 kV, 41 ~ 50 kHz

[0127] Distance between electrodes: 2.1 ~ 3.5 mm

[0128] Dielectric: Silicon resin 4 mm

[0129] Corona treatment frequency: 1 ~ 3 times

[0130] Other than performing corona discharge treatment instead of primer, the other processes were the same as in Example 1.

[0132] [Example 6]

[0133] In Example 1, when forming a release paper layer made of polyethylene on the adhesive layer, an embossed release paper was used. To emboss the polyethylene release paper sheet, a male roller and a female roller, each having rounded protrusions, were engaged and rotated, and the sheet was passed between them for processing. At this time, heat suitable for the characteristics of the material was applied to perform the embossing process by heat pressing.

[0135] [Example 7]

[0136] In Example 1, when forming a release paper layer made of polyethylene on the adhesive layer, a release paper with a silicone-coated emboss was used. As in Example 6, a release paper layer was formed using a release paper that had been embossed and then treated with silicone on the embossed surface.

[0137] Specifically, a silicone-based coating composition was prepared comprising, per 100 parts by weight of tetrahydrofuran (THF), 10 parts by weight of vinyl-terminated polydimethylsiloxane (Shin-Etsu Silicon / KS-847H) having a weight-average molecular weight of 300,000–400,000 g / mol and a polydispersity index of 1.8–2.2, 1 part by weight of a silicone-based crosslinking agent (Shin-Etsu Silicon / X-92-122), 3 parts by weight of a platinum-based catalyst (Shin-Etsu Silicon / PL-50T), and 10 parts by weight of a silicone-based compound (MCR-V41). Subsequently, the prepared silicone-based coating composition was applied at 2.5 g / m² on the embossed surface of an embossed polyethylene release liner. 2 It was applied to a thickness of 0.1 mm. Afterward, the applied silicone-based coating composition was dried and cured at 130°C for 1 minute, and then aged at 50°C for 24 hours to produce a silicone-release embossed release paper (thickness 0.1 mm).

[0139] [Example 8]

[0140] In Example 1, when forming a release paper layer made of polyethylene on the adhesive layer, a release paper with an embossed surface coated with fluoropolymer was used. As in Example 6, a release paper layer was formed using a release paper that had been treated with a fluoropolymer on the embossed surface after embossing.

[0141] Specifically, 2.85 g of methyl methacrylate (MMA, Samcheon Chemical, 99%), 0.15 g of 3-methacryloylpropyl trimethoxysilane (SZ-6030, Dow Corning), 0.02 g of 2,2'-azobis(4-methoxy-2,4-dimethyl vareronitrile) (V-70, Wako Pure Chemicals), and 12 g of isophorone (Sigma-Aldrich) were added to a 4-neck reactor and polymerized at 60°C for 6 hours to prepare a polymer binder. 5 g of PVDF (Alfa Aesar) as a fluorine-based polymer, 0.8 g of the above polymer binder, and 28 g of the organic solvent isophorone (Sigma-Aldrich) were mixed to prepare a fluorine-based coating composition with a solid content of 16 wt%. Subsequently, 2.5 g / m² of the prepared fluorine-based coating composition was applied to the embossed surface of an embossed polyethylene release liner heated to 120°C. 2 It was applied to a thickness of 0.1 mm. Afterward, it was dried and cured for 10 minutes, and then aged at room temperature for 24 hours to produce a fluorine-release embossed release paper (thickness 0.1 mm).

[0143] [Example 9]

[0144] The procedure was carried out as in Example 5, but in addition to TINUVIN 400 and TINUVIN 477, myristic acid (Daejeong Hwakum Co., Ltd., KR) was added when manufacturing the polyurethane outer film prior to corona discharge treatment. Specifically, when diluting the polyurethane, 1.5 parts by weight of TINUVIN 400, 2.5 parts by weight of TINUVIN 477, and 0.2 parts by weight of myristic acid were homogeneously mixed relative to 100 parts by weight of polyurethane solid content, and then applied to one surface of the carrier film layer to form an outer film.

[0146] [Experimental Example 1]

[0147] The adhesive strength of skin protection patch samples for outdoor activities according to the examples, etc., was measured on a stainless steel (SUS304) substrate in accordance with ASTM-D3330, and the results are shown in Table 1 below. Comparative Example 1 was prepared as in Example 1, but TINUVIN® 400 and TINUVIN® 477 were mixed into the adhesive composition without mixing with polyurethane. That is, when preparing the adhesive composition, 5 parts by weight of TINUVIN® 400 and TINUVIN® 477 were mixed in a weight ratio of 1:3, and polydimethylsiloxane (Vi(CH3)2SiO-[(CH3)2SiO] having vinyl groups at both ends n -Si(CH3)2Vi, n is 80) 35 parts by weight, hydride-terminated polydimethylsiloxane (H(CH3)2SiO-[(CH3)2)SiO)] m -Si(CH3)2H, m is 50) 1 part by weight, trimethylsiloxysilicate 45 parts by weight, 1-ethylcyclohexanol 0.1 parts by weight, corticosteroid 10 parts by weight, polyvinylidene fluoride (PVDF) 1 part by weight, and polytetrafluoroethylene (PTFE) 5 parts by weight were mixed to prepare a silicone adhesive layer. This was applied onto an outer film to form a silicone adhesive layer.

[0148] division Adhesive layer thickness (mm) Adhesion (gf / in) Example 1 0.02 3800 0.08 3820 Example 2 0.02 3750 0.08 3800 Example 3 0.02 3830 0.08 3850 Example 5 0.02 3790 0.08 3810 Example 9 0.02 3820 0.08 3870 Comparative Example 1 0.02 2400 0.08 2650 0.31 3450

[0149] For thicknesses of 0.02 mm and 0.08 mm, the adhesive layers according to Examples 1, 2, 3, 5, and 9 exhibited superior adhesive strength compared to the adhesive layer according to Comparative Example 1. However, when the thickness of the patch according to Comparative Example 1 was set to 0.31 mm, the adhesive strength increased; yet, due to the characteristics of the patch for outdoor activities, if the thickness of the adhesive layer exceeded 0.3 mm, the overall thickness of the patch became excessively thick when considering the outer film layer, etc., resulting in a sharp decline in preference as it did not blend evenly with sunscreen, cosmetics, etc., and thus impaired the aesthetics (see Experimental Example 2 below).

[0151] [Experimental Example 2]

[0152] Twenty-five adult male and female panelists who frequently use golf courses evaluated patches (2 cm in width and height) according to the examples, etc., using a 5-point scale for adhesiveness, satisfaction with thickness, transparency, satisfaction with appearance upon attachment, and overall preference. The release liner of the patch was removed, the adhesive layer was attached to facial skin exposed to sunlight, the carrier film layer was removed, and the evaluation was conducted. Table 2 below shows the results (arithmetic mean).

[0153] division Adhesive layer thickness (mm) adhesive Thickness satisfaction transparency Satisfaction with appearance when attached Overall preference Example 1 0.02 4.5 4.6 4.7 4.2 4.6 0.08 4.4 4.2 4.2 3.9 4.2 Example 2 0.02 4.6 4.5 4.5 4.3 4.5 0.08 4.7 4.1 4.2 4.0 4.0 Example 3 0.02 4.5 4.7 4.7 4.1 4.6 0.08 4.6 4.2 4.1 3.9 4.2 Example 4 0.02 4.6 4.5 4.5 4.5 4.4 0.08 4.4 4.1 4.1 4.2 4.1 Example 5 0.02 4.7 4.8 4.9 4.8 4.8 0.08 4.8 4.3 4.1 4.2 4.2 Example 9 0.02 4.3 4.6 4.8 4.4 4.6 0.08 4.7 4.2 4.2 4.1 4.3 Comparative Example 1 0.02 1.9 4.3 2.3 2.6 2.7 0.08 2.3 4.1 1.8 2.2 2.1 0.31 4.4 1.2 0.4 0.5 0.8

[0154] In the case of the patches of Examples 1, 2, 3, 4, 5, and 9, the adhesiveness was good, the thickness satisfaction was excellent, and the transparency was high, so the panels perceived them as transparent, and accordingly, the satisfaction with appearance and overall preference scores were high when attached. In the case of Comparative Example 1, when the adhesive layer thickness was 0.02 and 0.08 mm, the thickness satisfaction was high, but because a UV blocking component was mixed into the adhesive layer, the adhesiveness decreased and the transparency dropped sharply, and consequently, the satisfaction with attachment and overall preference also dropped significantly. When the adhesive layer thickness of Comparative Example 1 was 0.31 mm, the adhesiveness was maintained, but it was found that the thickness was excessively thick, so it did not blend evenly with sunscreen, cosmetics, etc., and was unsuitable for outdoor patches as it compromised the aesthetics.

[0156] [Experimental Example 3]

[0157] The UV blocking rate of the patches according to Examples 1, 2, 3, 5, and 9 was measured using the KS K 0850:2023 UV blocking performance test method. In addition, to compare the effects under different conditions, patches according to comparative examples were prepared as follows. Specifically, comparative examples were prepared by varying the amount of triazine-based UV absorber added relative to 100 parts by weight of polyurethane solids during polyurethane dilution in Example 1, as shown in Table 3 below (in each example and each comparative example, the thickness of the polyurethane outer film layer was approximately 3 μm).

[0158] For the patches according to each comparative example, the UV blocking rate was measured using the UV blocking performance test method as described above. The results are shown in Table 4 below.

[0159] In addition, the quality of each outer film was evaluated. Three experts were commissioned to evaluate whether it was suitable for skin adhesion in terms of transparency and physical properties (such as the elasticity characteristic of polyurethane). The results are listed in Table 4.

[0160] division 400 parts by weight of TINUVIN TINUVIN 477 parts by weight TinoSorb weight part Comparative Example 2 0.4 2.5 - Comparative Example 3 2.2 2.5 - Comparative Example 4 1.5 0.6 - Comparative Example 5 1.5 2.9 - Comparative Example 6 - - 0.9 Comparative Example 7 - - 3.2 Comparative Example 8 - 1.0 1.5 Comparative Example 9 - 1.0 2.4 Comparative Example 10 - 0.6 2.0 Comparative Example 11 - 1.7 2.0

[0162] division UV protection rate Outer film transparency, physical properties UVA (315-400nm) UVB (290-315nm) Example 1 92.1 92.3 O Example 2 93.3 91.2 O Example 3 95.7 92.4 O Example 5 93.2 92.1 O Example 9 98.5 96.7 O Comparative Example 2 89.4 53.2 O Comparative Example 3 92.0 91.4 X Comparative Example 4 50.4 88.1 O Comparative Example 5 92.5 90.2 X Comparative Example 6 49.7 51.2 O Comparative Example 7 91.3 90.2 X Comparative Example 8 48.2 61.5 O Comparative Example 9 90.4 87.4 X Comparative Example 10 93.8 90.7 O Comparative Example 11 94.7 90.9 X

[0163] It was found that the polyurethane outer films according to the examples exhibited a uniform UV blocking effect against both UVA and UVB despite having a thickness of 3 μm. In particular, it was confirmed that the physical properties of the polyurethane outer films, such as transparency and elasticity, were suitable for use in skin application. Among the outer films according to the comparative examples, it was found that in the case of the films according to Comparative Examples 3, 5, 7, 9, and 11, the administration of an excessive amount of triazine-based compounds exceeding a certain amount caused cloudiness in the film, leading to a decrease in transparency and a decrease in the elasticity of the film layer, thereby deteriorating the physical properties. In such cases, the quality of the outer film deteriorated to the point where it was difficult to use for skin application. Furthermore, as can be seen from other comparative examples, it was found that when the content of triazine-based compounds is insufficient, it does not adequately block either UVA or UVB.

[0165] [Experimental Example 4] Comparison of Process Efficiency Between Corona Treatment and Primer Treatment

[0166] The process efficiency of the primer treatment on the polyurethane outer film according to Example 1 and the corona discharge treatment according to Example 5 was compared. In the case of the primer treatment process, it took approximately 3 hours or more, including the preparation time for manufacturing the primer composition, the time for applying the primer composition, and the time for thickness adjustment. On the other hand, in the case of the corona discharge treatment, it took approximately 1 hour and 10 minutes, including the time for setting the treatment conditions of the corona treatment device and the time for discharge treatment inside the device, which reduced the time by approximately 1 hour and 50 minutes compared to the treatment with the primer composition. In other words, it was confirmed that modifying the polyurethane film layer through corona discharge treatment is significantly more efficient than the primer treatment process.

[0168] [Experimental Example 5] Release force test upon removal of release paper

[0169] A release force test was conducted while removing the release liner of the patch according to the examples from the adhesive layer. The release force required to remove the release liner immediately after manufacturing the patches according to Examples 1, 6, 7, and 8 and after 3 months was measured using an AR-1000 TLMI (ChemInstruments, US). The measurement conditions were set as an angle of 90 degrees, a speed of 300 inch / min, and a unit / specification of gf / 25mm.

[0170] As a result, the release force required to remove the release liner in the patch of Example 1 was 20 gf / in immediately after manufacturing, and increased to 120 gf / in after 3 months. In the patch of Example 6, the release force required to remove the release liner was 21 gf / in immediately after manufacturing, but was 38 gf / in after 3 months. In the patch of Example 7, the release force required to remove the release liner was 20 gf / in immediately after manufacturing, but was 31 gf / in after 3 months. In the patch of Example 8, the release force required to remove the release liner was 19 gf / in immediately after manufacturing, but was 21 gf / in after 3 months.

[0171] Release liners or release films coated on silicone adhesive layers generally have problems such as failing to release properly and sticking after a long time, or requiring excessive release force, which reduces the adhesive strength of the adhesive layer; consequently, it was difficult to launch products using silicone adhesives, such as skin care products. The release liners of Examples 6, 7, and 8 according to one aspect of the present invention maintain a low release force even after a long period of three months, so it can be seen that the disadvantages of existing release liners or release films have been significantly overcome.

Claims

Claim 1 A skin protection patch for outdoor activities comprising: a carrier film layer released with fluorine or silicone; a transparent outer film layer comprising polyurethane laminated on the carrier film layer; an adhesive layer laminated on the transparent outer film layer; and a release liner laminated on the adhesive layer to protect the adhesive strength of the adhesive layer and removable according to the user's intent, wherein the transparent outer film layer comprises polyurethane and a triazine-based ultraviolet absorber, and the transparent outer film layer is modified by corona discharge treatment. Claim 2 A skin protection patch for outdoor activities according to claim 1, wherein the transparent outer film layer comprises 0.5 to 10 parts by weight of a triazine-based ultraviolet absorber. Claim 3 A skin protection patch for outdoor activities according to claim 1, wherein the thickness of the transparent outer film layer is 1 μm or more and less than 5 μm. Claim 4 A skin protection patch for outdoor activities according to claim 1, wherein the triazine-based UV absorber comprises a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-didecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine. Claim 5 A skin protection patch for outdoor activities according to claim 1, wherein the triazine-based UV absorber comprises a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-didecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine in a weight ratio of 1:1 to 1:

5. Claim 6 A skin protection patch for outdoor activities according to claim 1, wherein the triazine-based ultraviolet absorber comprises bis-ethylhexyloxyphenol methoxyphenyl triazine. Claim 7 A skin protection patch for outdoor activities according to claim 1, wherein the triazine-based ultraviolet absorber comprises 0.5 to 3 parts by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine based on 100 parts by weight of the polyurethane. Claim 8 A skin protection patch for outdoor activities according to claim 1, wherein the triazine-based ultraviolet absorber comprises 2 parts by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine and 1 part by weight of 2,4,6-tris[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine. Claim 9 A skin protection patch for outdoor activities according to claim 1, wherein the thickness of the outer film layer containing the polyurethane is 1 μm or more and less than 5 μm. Claim 10 A skin protection patch for outdoor activities according to claim 1, wherein one side of the transparent outer film layer is coated with a primer or has a polar group introduced to improve adhesion with the adhesive layer. Claim 11 A skin protection patch for outdoor activities according to claim 1, wherein the adhesive layer is a silicone-based adhesive layer with enhanced adhesion. Claim 12 A skin protection patch for outdoor activities according to claim 1, wherein the release layer has an embossed structure on one side. Claim 13 A skin protection patch for outdoor activities according to claim 1, wherein the release layer has one side having an embossed structure, and one side of the embossed structure is released with fluorine or silicone. Claim 14 S1) a step of manufacturing a carrier film layer that is released with fluorine or silicone; S2) a step of manufacturing a transparent outer film layer comprising polyurethane that is laminated on the carrier film layer; S3) a step of performing corona discharge treatment on the transparent outer film layer; S4) a step of forming an adhesive layer laminated on the transparent outer film layer; and S5) a step of forming a release liner layer on the adhesive layer; comprising a method for manufacturing a skin protection patch for outdoor activities.

Images