Nail wear adhesive and method of making same

Abstract

The application discloses a nail wearing glue and a preparation method thereof, and belongs to the field of nail products. The product is different from the existing wearing nail or nail glue oil. Through the collocation of specific components, a soft glue intermediate can be formed by heat curing, and has a certain strength. The glue intermediate can be cut or dropped / sprayed into different thicknesses and sizes by using a mold after being coated on a release material, is convenient to store and has a certain viscosity. Therefore, the user can use the back glue or soft nail sheet to perfectly match the intermediate on the nail. After the actual cutting size, only one irradiation under the UV nail lamp is needed to complete the curing. The wearing nail does not have an obvious heating feeling during the curing process, has high adhesion to the nail, and does not have an obvious yellowing phenomenon after curing. The final wearing glue product has high hardness and good flexibility, and the thickness can reach 300-2000 microns according to the actual requirements, so as to meet the needs of different users.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nail art products, in particular to a nail wearing glue and a preparation method thereof. BACKGROUND

[0002] With the development of economy, people are more and more accepting of nail art as a hand beauty technique, and taking nail art as a means of daily leisure and improving their own image. The existing nail art field generally involves two kinds of nail art products: wearing nails and nail polish glue. Among them, wearing nails are ready-made nail pieces, and these product types are numerous according to the preferences and inclinations of consumers, with various cutting sizes, materials and patterns. They only need to use an adhesive glue (commonly known as jelly glue) on the nails first, and then press and fit the wearing nails directly on the adhesive glue. This type of product is convenient and fast to use, and even at home, you can wear it yourself. However, this type of nail piece is generally printed by 3D printing technology, in order to ensure the quality and uniformity of the material, the specific size and thickness (generally not more than 1000 μm) must be limited. For users with special size and thickness requirements, further cutting is often required, but due to its high hardness, it is difficult to cut to the appropriate size, and the product is also prone to breakage and damage to the nails when the thickness is high. On the other hand, since the curvature of each user's finger nails is not the same, it is difficult for such ready-made products to ensure that each wearing nail can perfectly fit the nail, and the experience during use cannot be guaranteed. Nail polish glue is mostly UV gel material, and this type of product generally applies a layer of primer on the nails first, then applies a layer of gel on the primer using a brushing method, and uses a UV nail lamp to irradiate the coating to harden the gel, then continues to apply the second layer, the third layer… until the desired thickness. Compared with wearing nails, nail polish glue does not need to be cut because the nail is coated with nail polish before it hardens, and the fit with the nail is good, but it takes a long time to use because it needs to be applied layer by layer and cured. The user's fingers will have a significant burning sensation after being irradiated by the UV curing nail lamp multiple times, and the more layers applied, the more obvious the burning sensation. At the same time, due to the flowability of the UV gel material, the size changes after curing, and some grinding and cutting are still needed. Due to the limitations of the application method, the product is also difficult to achieve a relatively thick thickness, and the hardness and flexibility of the product obtained by layer-by-layer application are relatively general, and as the number of layers increases, the product after curing will also have a certain yellowing phenomenon.

[0003] On the other hand, the improvement and innovation of the nail products in the existing nail industry are only within the conventional range, and in the existing development society, the rise of some emerging industries also leads to the fact that the existing nail products cannot meet the demand. For example, in the animation photography industry, people often need to use some props for wearing nails, but these wearing nails often need to be thick and exaggerated in size to achieve a realistic effect, so these wearing nails often need to be coated with a layer of color glue polyester on the surface before wearing, and then cut again. However, this method not only takes time and effort, but also cannot achieve the quality of industrialized production products, and is very cheap. SUMMARY

[0004] Based on the defects of the prior art, the purpose of the present application is to provide a nail wearing glue which is different from the existing wearing nails or nail glue oil. The product is in the form of a colloid after preparation, can be formed into an intermediate body after heat curing, has a certain strength, and can be coated on a release material and then cut or dropped (and sprayed on the nail plate) to make different thicknesses and sizes (even with a release mold to prepare by pouring). It is convenient to store and carry like wearing nails. At the same time, the intermediate body is relatively soft and has a certain adhesion, so the user only needs to perfectly fit the intermediate body on the nail with the backing or soft nail plate according to the actual situation after cutting the size, and only needs to be irradiated once under the UV nail lamp (ultraviolet lamp) to complete the curing. The user's fingers do not feel obvious burning during the curing process, and the product does not appear obvious yellowing after curing. The final wearing glue product is hard and has good flexibility, the thickness can be up to 2000pm without breaking, and can meet the actual needs of different users.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is:

[0006] A nail wearing glue, the preparation raw materials include A component and B component;

[0007] The A component includes the following components by weight:

[0008] Hydroxyl thermosetting resin 10-50 parts, UV resin containing hydroxyl 50-90 parts, photoinitiator 0.2-3 parts, catalyst 0.01-0.5 parts;

[0009] The B component includes isocyanate;

[0010] The ratio of the molar amount of hydroxyl in the A component to the molar amount of isocyanate group in the B component is (0.9-1.1):1.

[0011] Although there are some products prepared by using different solidification forms of resin in the prior art, these products are mainly paint films and are not used on wearable glue, and do not involve the problems in use experience. The hardness or wear resistance of these products after solidification is mainly considered, and the thickness of the paint film is low, so the fast drying or yellowing problems are not involved.

[0012] The hydroxyl thermosetting resin and the hydroxyl-containing UV resin in the A component of the nail wearable glue can cooperatively crosslink and react with the isocyanate in the B component under heating, so that the product can be initially formed into an intermediate which can be conveniently carried, attached to the nail and cut and trimmed, and has certain strength and flexibility. Then, the hydroxyl-containing UV resin in the component continues to crosslink and react under ultraviolet light, thereby giving the product high hardness and high strength without introducing any polymer plastic, and meeting the needs of different users in terms of thickness and size.

[0013] In addition, the inventor can effectively reduce the heat release of the UV resin during the photo-crosslinking and curing reaction and inhibit the yellowing of the product by the preferred ratio of the two resins. If the content of the hydroxyl resin is insufficient, the above effect cannot be achieved, and the brittleness of the product after the photo-crosslinking and curing reaction is high, and the product is prone to breakage during use. If the content of the hydroxyl thermosetting resin is too high, the final hardness of the product is insufficient.

[0014] Under the above ratio of the hydroxyl thermosetting resin and the hydroxyl-containing UV resin, the molar ratio of the hydroxyl group and the isocyanate group in the component needs to be close, otherwise the isocyanate will be wasted or the hydroxyl group will remain, which may cause problems in the performance of the product. When the content of the hydroxyl group is too high, the hydroxyl group in the product is not fully reacted, which may cause the strength and chemical resistance of the product to decrease. When the isocyanate is excessive, the hardness of the product after curing may be too high, and the toughness may be insufficient.

[0015] When the molar ratio of the functional resin and the isocyanate is 1:1, the hydroxyl thermosetting resin and the hydroxyl-containing UV resin can both theoretically undergo a curing reaction, and the excessive isocyanate will not cause the quality of the product to decrease. In actual production, the performance of the product prepared within the above ratio range is relatively stable, so this range is also allowed.

[0016] Preferably, the hydroxyl thermosetting resin is at least one of a hydroxyl acrylic resin, a hydroxyl alkyd resin and a hydroxyl polyester resin.

[0017] More preferably, the hydroxyl thermosetting resin is a hydroxyl acrylic resin.

[0018] More preferably, the hydroxyl acrylate resin can be at least one of ACR6602, ACR6688 produced by Tongde Chemical Co., Ltd., RLT-780-80, RLT-790-70 produced by Yu Da Foshan Runli Special Material Co., Ltd., M7900, M7570, M3285 produced by Dongguan Boyuan New Material Co., Ltd., PAR-1526B-60, PAR-1159-70, PAR-1569-80 of Shenzhen Jia Sheng Da Polymer Material Co., Ltd., and the like, while the hydroxyl acrylate resin is not limited to the above-mentioned types, and the hydroxyl acrylate resin achieving the same effect is within the protection scope of the present application. The hydroxyl acrylate resin can cross-link with isocyanate and give the product and intermediate specific mechanical effect, while the resin has high stability, effectively ensuring the color effect of the product. In the prior art, not all hydroxyl thermosetting resins are suitable for use in the product of the present application. If not properly selected, the product may have a certain degree of yellowing and it is difficult to achieve a comfortable temperature effect.

[0019] The inventors found that when the hydroxyl acrylate resin is selected, the performance of the product after heat curing is better.

[0020] Preferably, the hydroxyl-containing UV resin is at least one of a hydroxyl-containing polyurethane acrylate, a hydroxyl-containing polyester acrylate, and a hydroxyl-containing acrylate.

[0021] More preferably, the hydroxyl-containing UV resin is a hydroxyl-containing polyurethane acrylate.

[0022] More preferably, the hydroxyl-containing polyurethane acrylate can be at least one of 8465 produced by Guangdong Lankao New Material Co., Ltd., EBECRYL 4764 produced by Zhanxin Resin (China) Co., Ltd., W2395, W23951, W2396 produced by Guangzhou Wuxing Material Technology Co., Ltd., and SD1000, SD1010 produced by Guangzhou Songda New Material Technology Co., Ltd., while the hydroxyl-containing polyurethane acrylate is not limited to the above-mentioned types, and the hydroxyl-containing polyurethane acrylate achieving the same effect is within the protection scope of the present application.

[0023] Similar to the hydroxyl thermosetting resin, the product prepared by selecting the above-mentioned hydroxyl-containing polyurethane acrylate has better performance, and can effectively give the product sufficient strength and hardness during light cross-linking and curing. In this process, the exothermic degree is lower than that of other types, and the user experience is better.

[0024] The above-mentioned preferred hydroxyl thermosetting resin and hydroxyl-containing UV resin have stable properties and high compatibility, and can effectively react in the heat curing reaction and light cross-linking and curing reaction.

[0025] Preferably, the mass ratio of the A component and the B component is (2-4):1.

[0026] Preferably, the A component of the nail wear glue further comprises 0.1-20 parts of UV resin without hydroxyl and 0.1-10 parts of acrylic monomer.

[0027] The introduction of part of conventional UV resin and monomer in the components of the nail wear glue can further optimize the flexibility and hardness of the product after photocrosslinking curing, and further weaken the yellowing degree, and meanwhile, the relative content of the other two resin components is reduced, and the hardness of the product after thermal curing can be adjusted, so that the intermediate obtained is more suitable for cutting and trimming.

[0028] It should be particularly pointed out that, in order to provide a larger use range of the product, other resins can be introduced into the components of the nail wear glue as binding agents, dispersants, colorants, etc., and these resins can or can not have crosslinking reaction with isocyanate as long as the functional effects of other components are not reduced.

[0029] More preferably, the UV resin without hydroxyl is at least one of polyurethane acrylate, polyester acrylate, pure acrylate, and epoxy acrylate.

[0030] More preferably, the polyurethane acrylate can be at least one of 8462 and 846 produced by Baojun Chemical Co., Ltd. of Zhaoqing, 2108, 2522, and 2102A produced by Baojun Chemical Co., Ltd. of Zhaoqing, 6008 produced by Covestro Co., Ltd. of Germany, SW1322 produced by Guangzhou Sanwang Chemical Material Co., Ltd., and SJ2202 produced by Guangdong Haohui New Material Co., Ltd.

[0031] More preferably, the A component of the nail wear glue comprises 4-6 parts of UV resin without hydroxyl.

[0032] More preferably, the A component comprises the following components by weight:

[0033] hydroxyl thermal curing resin 10-40 parts, hydroxyl-containing UV resin 60-80 parts, 4-6 parts of UV resin without hydroxyl, photoinitiator 0.2-0.4 parts, and catalyst 0.01-0.1 parts.

[0034] After screening, the inventors found that the intermediate formed after thermal curing of the product prepared in the above preferred ratio has good strength and high flexibility, and can be effectively attached to the nails, and the product after photocrosslinking curing reaction has higher hardness and better flexibility, and the yellowing degree of the product is lower.

[0035] More preferably, the acrylic monomer can be at least one of EM90, EM315 produced by Changxing Chemical Industry Co., Ltd. of Taiwan, China, HEMA produced by Mitsubishi Rayon Co., Ltd. of Japan, L-61039, L-61040, L-61018 produced by Guangdong Luoke Road New Material Co., Ltd., HPMA, IBOA, EOEOEA produced by Sanwang Chemical Material Co., Ltd.

[0036] Preferably, the photoinitiator is a free radical polymerization initiator, and the weight fraction of the free radical polymerization initiator is 0.2-0.4 parts.

[0037] More preferably, the free radical polymerization initiator includes at least one of a cleavage type photoinitiator and a hydrogen abstraction type photoinitiator.

[0038] More preferably, the free radical polymerization initiator has an ultraviolet light absorption peak at 300-400 nm.

[0039] More preferably, the free radical polymerization initiator is at least one of a TPO initiator, a TPO-L initiator, a 1173 initiator, an 819 initiator, an MBF initiator, a BDK initiator, a BP initiator, an ITX initiator, a DETX initiator, and an EMK initiator.

[0040] More preferably, the free radical polymerization initiator is at least one of JRCURE 1108, JRCURE 1104, JRCURE 1110, etc. produced by Tianjin Jiuri New Material Co., Ltd., Omnirad MBF, Omnirad TPO, Omnirad TPO-L, Omnirad 184, etc. produced by BASF, and GR-MBF, GR-TPO, GR-TPO-L, GR-184, etc. produced by Hubei Guren Technology Co., Ltd.

[0041] More preferably, the free radical polymerization initiator has an ultraviolet light absorption peak at 350-400 nm.

[0042] More preferably, the free radical polymerization initiator is at least one of a TPO initiator and a TPO-L initiator.

[0043] More preferably, the free radical initiator is at least one of JRCURE 1108 and JRCURE 1110 produced by Tianjin Jiuri New Material Co., Ltd., and Omnirad TPO and Omnirad TPO-L produced by BASF.

[0044] Since the content of the photoinitiator is increased, the light cross-linking reaction speed of the product component is increased, the curing efficiency is improved, but at the same time, the peak temperature of the product in the curing process caused by heat release is also increased, therefore, only by using an appropriate amount of photoinitiator, the light cross-linking curing reaction rate of the product can be faster, the user's burning sensation is more unobvious when curing for a short time, and meanwhile, the appropriate amount of photoinitiator can further reduce the heat emission of the product during the light cross-linking curing reaction.

[0045] It should be noted that the photoinitiator described in the present application is not limited to the above-mentioned types or specific goods, as long as the same technical effect can be achieved, they can be used instead, and they are within the protection scope of the present application.

[0046] Preferably, the catalyst is at least one of an organic amine, an organic metal compound.

[0047] Preferably, the A component of the nail wear glue further comprises a processing aid 0.3-5 parts.

[0048] Preferably, the processing aid is at least one of a defoaming agent, a wetting agent, a leveling agent and a water removal agent.

[0049] More preferably, the defoaming agent is at least one of a silicone defoaming agent and a non-silicone defoaming agent, the wetting agent is at least one of a silicone wetting agent and a fluorine-based substrate wetting agent, the leveling agent is at least one of a silicone leveling agent and a non-silicone leveling agent, and the water removal agent is an isocyanate water removal agent.

[0050] Preferably, the A component of the nail wear glue further comprises 0.1-30 parts of a solvent.

[0051] In different use cases (for example, the user applies different thicknesses of the primer or selects to stack one more PU film when using the product), the components of the nail wear glue described in the present application can further add an appropriate amount of solvent to adjust the viscosity, and the use experience is better.

[0052] Another object of the present application is to provide a preparation method of the nail wear glue, comprising the following steps:

[0053] (1) uniformly mixing the A component and the B component and performing defoaming treatment, then performing glue dropping or compression molding treatment, and after hot curing at 80-130 DEG C to form an intermediate;

[0054] (2) placing the intermediate under a UV lamp for 1-2 min to obtain the nail wear glue.

[0055] The preparation method of the nail wear glue has simple steps, the intermediate can realize industrialized scale production, and when the intermediate is used as a product, only needs to be attached to a soft nail sheet or a primer, and placed under a UV lamp to perform a photocrosslinking curing reaction, so that the nail wear glue is obtained, and the time consumption is far shorter than that of the existing nail polish glue prepared by layer-by-layer coating and curing.

[0056] Preferably, the heat curing forming can be replaced by natural curing forming at room temperature, and the time of the natural curing forming is 3-6h.

[0057] The intermediate of the wear nail glue can also be naturally cured and formed at room temperature, and is convenient and fast to process and transport.

[0058] The nail wear glue provided by the application is different from the existing wear nail or nail polish, and through the matching of specific components, a soft glue intermediate with certain strength can be formed by heat curing, the intermediate can be pre-cut or dropped (or sprayed) into different thicknesses and sizes through a mold, convenient to store and carry, and has certain adhesion, so that the user can perfectly attach the intermediate on the nail by cooperating with a back glue or a soft nail sheet, cut the size according to the actual situation, and only needs to be irradiated once under a UV manicure lamp to complete the curing, the user's finger will not appear obvious burning feeling in the curing process, keeps high adhesion with the nail, and will not appear obvious yellowing phenomenon after curing, and finally obtained wear glue product has large hardness and good flexibility, and the thickness can reach 300-2000μm (the product can reach 3000μm in the case of special purpose), and meets the actual needs of different users. DETAILED DESCRIPTION

[0059] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples and comparative examples, and the purpose is to understand the content of the present application in detail, rather than limit the present application. All other examples obtained by those skilled in the art without creative labor fall within the protection scope of the present application. The experimental reagents and instruments designed in the present application and the comparative examples are common ordinary reagents and instruments, unless otherwise specified.

[0060] It should be noted that the specification and claims of the present application and the above-mentioned terms "include", "contain" and "have" and any deformation thereof are intended to cover non-exclusive inclusion. For example, the process, method, system, product or equipment including a series of steps or units is not limited to the listed steps or units, but optionally also includes the steps or units not listed, or optionally also includes other steps or units inherent to these processes, methods, products or equipment. In the claims, specification of the present application, the terms such as "first" and "second" and the like relationship terms are only used to distinguish one entity / operation / object from another entity / operation / object, and do not necessarily require or imply any such actual relationship or order between the entities / operations / objects.

[0061] In the present application, the preparation raw materials of the nail wearing adhesive include A component and B component;

[0062] The A component includes the following components by weight:

[0063] Hydroxyl thermosetting resin 10-50 parts, hydroxyl-containing UV resin 50-90 parts, photoinitiator 0.2-3 parts, catalyst 0.01-0.5 parts;

[0064] The B component includes isocyanate;

[0065] The ratio of the molar amount of hydroxyl in the A component to the molar amount of isocyanate group in the B component is (0.9-1.1):1.

[0066] In addition, as a preferred embodiment of the present application, the A component further contains hydroxyl-free UV resin, acrylic monomer, processing aid and solvent; the processing aid is defoaming agent, wetting agent, leveling agent, water removal agent.

[0067] As a preferred embodiment of the present application, the hydroxyl thermosetting resin is at least one of hydroxyl acrylic resin, hydroxyl alkyd resin, hydroxyl polyester resin.

[0068] Further, in order to balance the use experience, mechanical properties and appearance performance of the product, the hydroxyl thermosetting resin is selected as hydroxyl acrylic resin.

[0069] Further, at least one of ACR6602, ACR6688 produced by Tongde Chemical Co., Ltd., RLT-780-80, RLT-790-70 produced by Yuuda Foshan Runli Special Material Co., Ltd., M7900, M7570, M3285 produced by Dongguan Boyuan New Material Co., Ltd., PAR-1526B-60, PAR-1159-70, PAR-1569-80 of Shenzhen Jia Shengda Polymer Material Co., Ltd. can be selected.

[0070] As a preferred embodiment of the present application, the hydroxyl-containing UV resin is at least one of a hydroxyl-containing polyurethane acrylate, a hydroxyl-containing polyester acrylate, and a hydroxyl-containing acrylate,

[0071] Further, in order to achieve lower exothermic effect of the product during photocrosslinking curing and to balance the strength and hardness, the hydroxyl-containing UV resin is selected to be a hydroxyl-containing polyurethane acrylate.

[0072] Further, at least one of 8465 produced by Guangdong Lanke Road New Material Co., Ltd., EBECRYL 4764 produced by Zhanxin Resin (China) Co., Ltd., W2395, W23951, and W2396 produced by Guangzhou Wuxing Material Technology Co., Ltd., and SD1000 and SD1010 produced by Guangzhou Songda New Material Technology Co., Ltd. can be selected.

[0073] In the two preferred resin combinations, the contained hydroxyl groups can cooperate with the isocyanate in the B component to occur crosslinking thermal curing reaction under heating conditions, so that the product can be initially formed into an intermediate that can be conveniently carried, fitted to the nail, and cut and trimmed, and has certain strength and flexibility; then under ultraviolet light irradiation, the hydroxyl-containing polyurethane acrylate in the component continues to occur photocrosslinking curing reaction, thereby giving the product high hardness and high strength without introducing any polymer plastic, while involving multiple thicknesses and sizes to meet the needs of different users. On the other hand, the two resins can ensure the rapid drying property of the product during curing and the low exothermic property during drying, so that the user does not have a significant peak heating sensation during wearing and curing, and the appearance performance of the product after curing is good without obvious color difference change and yellowing phenomenon.

[0074] As a preferred embodiment of the present application, the hydroxyl-free UV resin is a polyurethane acrylate, and further can be at least one of 8462 and 846 produced by Baojun Chemical Co., Ltd. of Zhaoqing, 2108, 2522, and 2102A produced by Cognis (Germany) Co., Ltd., 6008 produced by Cognis (Germany) Co., Ltd., SW1322 produced by Guangzhou Sanwang Chemical Material Co., Ltd., and SJ2202 produced by Guangdong Haohui New Material Co., Ltd.

[0075] As a preferred embodiment of the present application, the acrylic monomer can be at least one of EM90 and EM315 produced by Changxing Chemical Industry Co., Ltd. of Taiwan, China, HEMA produced by Mitsubishi Rayon Co., Ltd. of Japan, L-61039, L-61040, and L-61018 produced by Guangdong Lanke Road New Material Co., Ltd., and HPMA, IBOA, and EOEOEA produced by Sanwang Chemical Material Co., Ltd.

[0076] As a preferred embodiment of the present application, the photoinitiator is at least one of TPO initiator, TPO-L initiator, 1173 initiator, 819 initiator, MBF initiator, BDK initiator, BP initiator, ITX initiator, DETX initiator, EMK initiator.

[0077] Further, the photoinitiator is at least one of TPO initiator, TPO-L initiator.

[0078] More preferably, the photoinitiator is TPO-L initiator.

[0079] The photoinitiator is mainly used to initiate the photocrosslinking curing reaction of the resin raw material in the product of the present application. However, different types of photoinitiators have different initiation efficiencies and initiation rates. If not properly selected, it may cause the photocrosslinking curing reaction rate of the resin raw material to be unstable, causing the local time rate to be too high, at which time a large amount of heat is generated, resulting in a high peak exothermic content in the curing process, and the user's fingers feel hot. On the other hand, some photoinitiators have low initiation efficiency, so even if a large amount of content or a long crosslinking time is introduced, the final hardness of the product remains at a low level, and at the same time, it also causes waste of raw material cost (the price of photoinitiator is generally high).

[0080] More preferably, the TPO initiator, TPO-L initiator can be at least one of JRCURE 1108, JRCURE 1110 produced by Tianjin Jiurixin New Material Co., Ltd., Omnirad TPO, Omnirad TPO-L produced by BASF.

[0081] As a preferred embodiment of the present application, in the preparation raw material of the nail wearing glue, the A component comprises the following components by weight:

[0082] Hydroxyl thermosetting resin 10-40 parts, hydroxyl-containing UV resin 60-80 parts, 4-6 parts of UV resin not containing hydroxyl, photoinitiator 0.2-0.4 parts, catalyst 0.01-0.1 parts, acrylic monomer 0.1-3 parts, catalyst 0.01-0.1 parts, defoaming agent 0.5-1.5 parts, wetting agent 0.3-1 parts, leveling agent 0.1-0.3 parts, water removal agent 1-2 parts and solvent 0.1-30 parts.

[0083] In the A component, two resins relate to the various properties of the product, the hydroxyl thermosetting resin can reduce the degree of heat release of the UV resin containing hydroxyl group when the photo-crosslinking curing reaction occurs and inhibit the yellowing phenomenon of the product, if the content of the hydroxyl resin is insufficient, it is difficult to achieve the above effect, at the same time, the brittleness of the product is high after the photo-crosslinking curing reaction, and the product is prone to breakage during use; if the content of the hydroxyl thermosetting resin is too high, it will also easily lead to insufficient final hardness of the product. Under the condition that the ratio of the hydroxyl-containing thermosetting resin and the UV resin is certain, the introduction of a specific UV resin containing no hydroxyl group can effectively regulate the mechanical properties and yellowing resistance of the product, but if the introduction amount is too much, it will cause the performance of the product to decrease. On the other hand, when the addition amount of the photoinitiator is low, the photo-crosslinking reaction degree of the resin raw material is not complete, the hardness of the product is insufficient, and at the same time, it will also cause incomplete setting of part of the resin, which may cause the problem of uneven specifications in the later stage; if the addition amount of the photoinitiator is too high, it will also cause the temperature of the wearing adhesive product to increase during the curing process (the peak value is high), and the user experience is reduced, therefore, in order to achieve the best comprehensive performance and user experience of the product, the addition amount of the photoinitiator also needs to be considered.

[0084] In the present application, the preparation method of the nail wearing adhesive comprises the following steps:

[0085] (1) uniformly mix the A component and the B component and perform defoaming treatment, then perform glue dropping or pressure molding treatment, and after heat curing at 80-130 DEG C, an intermediate product is obtained;

[0086] (2) place the intermediate product under the ultraviolet lamp for 1-2 min, and the nail wearing adhesive is obtained.

[0087] The nail wearing adhesive of the present application is different from the similar functional products in the existing nail industry, due to the particularity of the components, it can be first prepared into a formed intermediate product with moderate strength and hardness, the product has processability and can be processed according to the needs of the user, then perfectly attached to the nail with the backing adhesive or the soft film (due to the particularity of the formula, the intermediate product has high adhesion to the film), and then photo-crosslinking secondary curing is performed, so that the product is more attached to the nail, the strength is improved, and the use convenience is significantly improved compared with the similar products.

[0088] As another preferred embodiment of the present application, the heat curing molding can be replaced by natural curing molding at room temperature, and the time of the natural curing molding is 3-6 h.

[0089] Since the product preparation raw material contains a thermosetting resin raw material, according to the difference of the preparation environment, the product can not be directly heated in the process of forming the intermediate, but can be equally selected as a form of natural slow curing at room temperature, which can make the intermediate remain plasticity for a long time, and the size, thickness, properties and the like thereof can be adjusted by the person skilled in the art according to the actual needs. On the other hand, the intermediate of the product of the present application can also be prepared by using existing common molding technologies such as 3D printing during the natural curing process (when the intermediate has strong plasticity).

[0090] As a preferred embodiment of the present application, the thickness of the nail wear glue of the present application is 300-3000 μm.

[0091] The nail wear glue of the present application can be directly designed as a conventional 300-1200 μm thickness specification according to the general situation of the nail industry due to the preferred formula, and the product meets the needs in terms of appearance, mechanical properties and use experience performance, and the product of the present application can be further increased in thickness to more than 1200 μm which cannot be achieved by traditional nail plates, and even to 3000 μm for some special occasions (such as decorative model props, etc.), and the product can still maintain good mechanical properties (even if high-thickness folding test is performed, no fracture occurs) and dimensional stability, and can still maintain good appearance performance at a relatively thick degree without obvious yellowing.

[0092] Examples 1-19

[0093] The preparation method of the nail wear glue of the present application includes the following steps:

[0094] (1) uniformly mix the A component and the B component and perform defoaming treatment, then perform compression molding treatment, and after heat curing at 100°C, an intermediate is obtained;

[0095] (2) place the intermediate under a UV lamp for 2 min, and the nail wear glue is obtained.

[0096] It should be particularly pointed out that the product of Example 2 is directly naturally cured at room temperature for 6 h to obtain the nail wear glue after obtaining the intermediate.

[0097] Comparative Examples 1-3

[0098] The difference between each comparative example and the example is only in the different component proportions.

[0099] The raw materials used in each example and comparative example are as follows, and the proportions of the raw materials are shown in Table 1.

[0100] Thermosetting resin: hydroxyl group

[0101] Hydroxyl acrylic resin, ACR6602, ACR6688 from De Chemical Co. Ltd.

[0102] Hydroxyl alkyd resin, 3370D-1 from Sanmu Group, Jiangsu.

[0103] Hydroxyl polyester resin, TOR-7815-70 from Jiashengda Polymer Material Co. Ltd., Shenzhen.

[0104] Hydroxyl epoxy resin, SM828 from Sanmu Group, Jiangsu.

[0105] Hydroxyl-containing UV resin:

[0106] Hydroxyl-containing polyurethane acrylate, 8211 from Baxh New Material Technology Co. Ltd.; 8465 from Lanke New Material Co. Ltd., Guangdong.

[0107] Hydroxyl-containing polyester acrylate, EB4266 from Zhanxin Resin (China) Co. Ltd.

[0108] Hydroxyl-containing epoxy acrylate, EB3700 from Zhanxin Resin (China) Co. Ltd.

[0109] Non-hydroxyl-containing UV resin:

[0110] Polyurethane acrylate, 8462 from Baxh New Material Technology Co. Ltd.

[0111] Acrylic monomer, EM90 from Changxing Chemical Industrial Co. Ltd., Taiwan, China.

[0112] Photoinitiator, JRCURE 1108 from Tianjin Jiuri New Material Co. Ltd.

[0113] Catalyst, Borchi KAT 24 produced by Borchers (Shanghai) Trading Co. Ltd.

[0114] Defoamer, BYK-054 produced by BYK.

[0115] Wetting agent, Borchi Gol 1375 produced by Borchers (Shanghai) Trading Co. Ltd.

[0116] Leveling agent, BYK-361N from BYK.

[0117] Water-removing agent, Borchers Addtive Ti produced by Borchers (Shanghai) Trading Co. Ltd.

[0118] Isocyanate: N 3390 produced by Bayer, Germany.

[0119] The commercially available raw materials used in each example and comparative example are all the same.

[0120] Meanwhile, the raw materials used in the products obtained in each embodiment and the comparative example are also the same when performing parallel experiments.

[0121] Table 1

[0122]

[0123]

[0124]

[0125] Note: The theoretical molar ratio of hydroxyl groups in the A component to isocyanate groups in the B component in each embodiment and the comparative example is 1:1, the above ratio is calculated based on 100% solid content, and the same curing agent is used, and the selected test resin is also a fixed parameter resin. Because the hydroxyl content of the hydroxyl resin is very different, the actual test of high hydroxyl and low hydroxyl can be used, and the above data is the test result of the high hydroxyl resin.

[0126] Effect example

[0127] When each embodiment and the comparative example is heat-cured, the nail is cut into samples of 5*3 cm and different thicknesses (300, 500, 800, 1200, 1500, 2000 and 3000 μm) and the following tests are performed:

[0128] (1) Hardness of the intermediate sample after heat-curing: the hardness of the intermediate sample is directly tested by using a Shore D hardness tester (the sample hardness is not related to the thickness, and the 1200 μm thick intermediate sample is uniformly used for testing);

[0129] (2) Flexibility test of the intermediate sample after heat-curing: the 3000 μm thick intermediate sample is mechanically folded by 180° along the long edge, and the surface condition of the sample (whether cracks appear) is observed;

[0130] (3) Yellowing phenomenon of the wear-resistant adhesive sample after photo-crosslinking curing: as the thickness of the wear-resistant adhesive sample increases, the yellowing phenomenon becomes more obvious. In order to verify the best performance of the wear-resistant adhesive product, the color difference Δb of the 3000 μm thick wear-resistant adhesive sample is directly tested by using a color difference meter, and the larger the value, the more obvious the yellowing phenomenon;

[0131] (4) Hardness of the wear-resistant adhesive sample after photo-crosslinking curing: as the wear-resistant adhesive product is irradiated under the ultraviolet lamp for a longer time, the hardness will slowly and continuously increase within a certain range. Therefore, the photo-crosslinking curing is performed by using the product of the present application for an average single irradiation time of 2 min by using a manicure lamp, and the hardness of the 1200 μm thick wear-resistant adhesive sample after photo-crosslinking curing is directly tested by using a Shore D hardness tester;

[0132] (5) The flexibility of the wearable adhesive sample after photocrosslinking and curing: fold the wearable adhesive sample of different sizes and thicknesses along the long edge by 180° mechanically, and observe the surface condition (because the strength of each test wearable adhesive sample after photocrosslinking and curing is high, and the pressure required for 180° folding of the actual 3000 μm thick sample by a mechanical arm is more than 5 times the pressure that the normal nail can bear, so only the wearable adhesive sample with a thickness of 2000 μm is tested); record the surface condition of the sample as intact without cracks, with cracks, and broken; it needs to be specially pointed out that for real wearable adhesive similar products, their thickness generally does not exceed 1000 μm, so at this thickness, the product needs to be intact without cracks to be recognized as meeting the current market use requirements, but for products with a thickness higher than 1000 μm, due to the physical limitations of the material itself, certain cracks may occur in the case of thicker products, but such cracks are obviously different from breaking, and it is also difficult to occur in actual use (because in actual conditions, thicker products are difficult to fold by 180°, and when stressed, they will be transmitted to the nail or fall off from the nail in advance), so as long as there is no breaking, it is also acceptable;

[0133] (6) Temperature test during photocrosslinking and curing: after the intermediate sample is irradiated under the ultraviolet lamp for 2 min, the bottom temperature of the obtained wearable adhesive sample with a thickness of 300 μm, 500 μm, 800 μm, and 1200 μm is directly tested by using a TCP-X multi-channel temperature recorder, and the bottom of the intermediate with a thickness of 1500 μm and 2000 μm is covered with a layer of 10 μm bottom adhesive and 10 μm PU film before ultraviolet irradiation (for wearable nails with a thickness of more than 1500 μm, similar to the existing commercially available nail sheet products, the bottom needs to be treated accordingly before actual application to ensure the comfort of the finger); after ultraviolet irradiation, the temperature (peak temperature) at the bottom of the adhesive is tested; the lower the temperature, the lower the user's burning sensation, and according to the market research and experimental statistics of the inventors, when the temperature during curing exceeds 55°C, the user's finger will have a significant burning sensation, and when the temperature is lower than this, the user can accept the temperature, and when the temperature is lower than 50°C, the user's finger experiences the best; and for products with a thickness of 3000 μm, the time required for photocrosslinking and curing has exceeded the time that the normal nail industry can accept, and the temperature reached has also exceeded the range of human body comfort, and needs to be pre-processed, so in order to simulate the actual product use process, this test only tests products with a thickness of up to 2000 μm;

[0134] (7) Shrinkage of wear adhesive sample after photocrosslinking curing: measure the size and thickness of each 2000 μm thickness intermediate sample before and after photocrosslinking curing directly, calculate the shrinkage of each wear adhesive sample (%) = (volume before photocrosslinking curing - sample volume after photocrosslinking curing) * 100%; since the shrinkage of wear adhesive product has certain correlation with thickness, the thicker the sample, the higher the shrinkage before and after photocrosslinking curing, therefore the thickest sample in test (6) is selected as the test sample of this test;

[0135] The test results are shown in Table 2.

[0136] Table 2

[0137]

[0138]

[0139]

[0140]

[0141] From Table 2, it can be seen that the intermediate obtained by heat curing of the nail wear adhesive of the present application can be cut into different sizes and thicknesses according to actual needs and has certain strength, and has good flexibility (the intermediate is a gel, and folding does not break at a thickness of 2000 μm); the product is convenient to transport, store, cut and adjust to fit the nail after molding; the yellowing color difference Δb of the product after light crosslinking curing is less than 10, the color difference stability is high, and the product after light crosslinking curing does not break even when mechanically folded at a thickness of 2000 μm; the Shore D hardness is above 70, and the rigidity and toughness are excellent; the light crosslinking curing time of the product is relatively short, and the temperature of the product (below a thickness of 1200 μm) after curing can be maintained within 55°C, and the user's fingers do not feel significantly hot (because the product of the present application takes a relatively short time during the ultraviolet curing process, and the temperature fluctuates greatly, and in the presence of a backing adhesive, the user's fingers feel different from actually touching the product, and according to market research and experimental testing by the inventor, the user's experience is good below 55°C), and except for the product of Example 4, the temperature of the other products is below 50°C, and the user's fingers have a better experience; at the same time, the product does not shrink significantly, and the degree of fit with the nail after ultraviolet light irradiation does not change. From the comparison of the products of Examples 4-7, Example 10 and Examples 13-15, it can be seen that the types of hydroxyl resin and UV resin containing hydroxyl groups have certain effects on the performance of the product, and the yellowing and final hardness performance of the product are best when hydroxyl acrylic resin and polyurethane acrylic UV resin containing hydroxyl groups are used; if non-optimal types of resin are selected, the degree of yellowing of the product may be high; from Examples 8-12, it can be seen that the ratio of hydroxyl resin to UV resin containing hydroxyl groups in the components of the nail wear adhesive of the present application has certain effects on the performance of the product, and when the preferred hydroxyl heat curing resin is 20-40 parts, and the UV resin containing hydroxyl groups is 60-80 parts, the product can have good flexibility before use, can be soft and well fitted to the nail surface during wear, and the hardness and toughness after curing can meet the requirements. In contrast, the product obtained in Comparative Example 1 does not contain hydroxyl resin, has high heat release and obvious yellowing, and breaks at a thickness of 800 μm; the components of the product of Comparative Example 3 contain hydroxyl resin, but the content is too low, and the effect of the examples cannot be achieved; the content of hydroxyl resin in the components of the product of Comparative Example 2 is too high, and the content of UV resin containing hydroxyl groups is insufficient, the hardness is not enough, and the product cannot be used to extend the nail (to extend a little from the front of the nail), and can only be used on the nail, and the range of use is narrow.

[0142] To verify the further preference of the photoinitiator in the nail wear adhesive component of the present application, a control experiment of the product was set up with different contents of the photoinitiator (while setting up a control group of other types of photoinitiators), other components and proportions, preparation methods and Example 7 were the same, the added amount of the photoinitiator was shown in Table 3, the 1200 μm thickness intermediate prepared from the component was irradiated under the ultraviolet lamp for 1.5 min and 2 min respectively, and the hardness of the product and the temperature after photocrosslinking and curing (2 min) were shown in Table 3.

[0143] Table 3

[0144]

[0145] The photoinitiator of the product of the present application is mainly used to initiate the photocrosslinking and curing reaction of the UV resin, and the inventor found that when other non-preferred types of photoinitiators were selected, the hardness change rate of the final wear adhesive product was lower and the final hardness was not high as a whole compared with the preferred specific type of photoinitiator. For the preferred photoinitiator of the present application, if the added content is low, the hardness of the wear adhesive product under the same ultraviolet lamp irradiation time is insufficient; and if the added content is too high, it will cause the temperature of the wear adhesive product to rise during the curing process (the peak value is high), and the user experience is reduced, therefore the comprehensive performance and use experience of the product is best when the added content is 0.2-0.4 parts.

[0146] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A nail wear adhesive, characterized by, The preparation raw material comprises A component and B component; The A component comprises the following components by weight: hydroxyl thermosetting resin 20~40 parts, hydroxyl-containing UV resin 60~80 parts, photoinitiator 0.2~0.4 parts, catalyst 0.01~0.5 parts; the hydroxyl thermosetting resin is hydroxyl acrylate resin; the hydroxyl-containing UV resin is hydroxyl-containing polyurethane acrylate; the photoinitiator in the A component is a free radical polymerization initiator, and the free radical polymerization initiator is at least one of TPO initiator and TPO-L initiator; The B component comprises isocyanate; The ratio of the molar amount of hydroxyl in the A component to the molar amount of isocyanate group in the B component is (0.9~1.1):

1.

2. The nail wear adhesive of claim 1 wherein, The mass ratio of the A component to the B component is (2~4):

1.

3. The nail wear adhesive of claim 1 wherein, The ultraviolet absorption peak of the free radical polymerization initiator is at 300nm~400nm.

4. The nail wear adhesive of claim 1 wherein, The catalyst in the A component is at least one of organic amine and organic metal compound.

5. The nail wear adhesive of claim 1 wherein, The A component of the nail wear adhesive further comprises 0.1~20 parts of UV resin without hydroxyl.

6. The nail wear adhesive of claim 5 wherein, The A component of the nail wear adhesive comprises 4~6 parts of UV resin without hydroxyl.

7. The nail wear adhesive of claim 6 wherein, The UV resin without hydroxyl is at least one of polyurethane acrylate, polyester acrylate, pure acrylate and epoxy acrylate.

8. The nail wear adhesive of claim 7 wherein, The A component comprises the following components by weight: hydroxyl thermosetting resin 20~40 parts, hydroxyl-containing UV resin 60~80 parts, 4~6 parts of UV resin without hydroxyl, photoinitiator 0.2~0.4 parts, catalyst 0.01~0.1 parts.

9. The nail wear adhesive of claim 1 wherein, The A component of the nail wear adhesive further comprises 0.1~10 parts of acrylic monomer.

10. The nail wear adhesive of claim 1 wherein, The A component of the nail wear adhesive further comprises 0.3~5 parts of processing aid.

11. The nail wear adhesive of claim 10 wherein, The processing aid is at least one of defoaming agent, wetting agent, leveling agent and water removal agent.

12. The nail wear adhesive of claim 11 wherein, The defoaming agent is at least one of silicone defoaming agent and non-silicone defoaming agent; the wetting agent is at least one of silicone wetting agent and fluorine-based substrate wetting agent; the leveling agent is at least one of silicone leveling agent and non-silicone leveling agent; and the water removal agent is isocyanate water removal agent.

13. The nail wear adhesive of claim 1 wherein, The A component of the nail wear adhesive further comprises 0.1~30 parts of solvent.

14. The method for preparing the nail-wearing gel according to any one of claims 1 to 13, characterized in that, The method comprises the following steps: (1) mixing the A component and the B component uniformly and performing defoaming treatment, then performing glue dropping or compression molding treatment, and then performing heat curing molding at 80~130℃ to obtain an intermediate; (2) placing the intermediate under ultraviolet lamp for 1~2min to obtain the nail wear adhesive.

15. The method for preparing the nail-wearing gel as described in claim 14, characterized in that, The heat curing molding step at 80~130℃ is replaced by natural curing molding step at room temperature, and the time of the natural curing molding at room temperature is 3~6h.

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