High-adhesion wear-resistant UV glue, preparation method and application thereof

Abstract

This invention belongs to the field of photocurable polymer materials technology, specifically relating to a high-adhesion, wear-resistant UV adhesive, its preparation method, and its application. The preparation method of the UV adhesive includes the following steps: polyglycerol and a diisocyanate compound are heated and reacted under the conditions of a catalyst and anhydrous diluent to obtain an isocyanate-terminated oligomer solution. Then, (meth)acrylate hydroxyl ester is added to continue the reaction, yielding a modified polyurethane acrylate. The obtained modified polyurethane acrylate is mixed uniformly with an active diluent monomer, vinyl MQ silicone resin, and a photoinitiator to obtain a high-adhesion, wear-resistant UV adhesive. The UV adhesive of this invention utilizes a specific modified polyurethane acrylate and vinyl MQ silicone resin for synergistic modification, which can simultaneously improve the adhesion, wear resistance, strength, toughness, and photocuring efficiency of the obtained UV adhesive.

Description

Technical Field

[0001] This invention belongs to the field of photocurable polymer materials technology, specifically relating to a high-adhesion, wear-resistant UV adhesive, its preparation method, and its application. Background Technology

[0002] With the development of the nail industry, the application of artificial nails is becoming increasingly widespread. Among them, UV-cured artificial nails have become the mainstream product in the market due to their advantages such as rapid curing, long-lasting adhesion, low odor, and ease of use. Their main components include acrylic resin or modified acrylic resin, active monomers, photoinitiators, and various additives. For example, patent document CN118175988 A describes a light-curable composition for nails or artificial nails, which contains the following components (A) to (D): (A) Component: a compound having a (meth)acryloyl group; (B) Component: a polythiol compound; (C) Component: a photoinitiator; (D) Component: a filler containing components (D-1) and (D-2), wherein components (D-1) and (D-2) are surface-treated fumed silica residues having specific surface features.

[0003] While using silica can improve the abrasion resistance and thixotropic properties of UV adhesives, its weak adhesion to the adhesive solution can easily lead to a decrease in the strength and toughness of the cured film. Although surface treatment with silane compounds can improve the compatibility between silica and the adhesive solution, silane modification significantly reduces the polarity of the modified product, which can easily lead to a decrease in the adhesion of the cured film. Summary of the Invention

[0004] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is a method for preparing a high-adhesion, wear-resistant UV adhesive.

[0005] Another object of the present invention is to provide a high-adhesion, wear-resistant UV adhesive prepared by the above method.

[0006] Another object of the present invention is to provide the application of the above-mentioned high-adhesion, abrasion-resistant UV adhesive in artificial nails.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A method for preparing a high-adhesion, abrasion-resistant UV adhesive includes the following preparation steps:

[0009] (1) Polyglycerol and diisocyanate compound were heated and reacted under the conditions of catalyst and anhydrous diluent to obtain an isocyanate-terminated oligomer solution;

[0010] (2) Add (meth)acrylate hydroxy ester to the oligomer solution in step (1) and continue the reaction. After the reaction is completed, remove the solvent to obtain modified polyurethane acrylate.

[0011] (3) The modified polyurethane acrylate obtained in step (2) is mixed evenly with reactive diluent monomer, vinyl MQ silicone resin and photoinitiator to obtain a high-adhesion wear-resistant UV adhesive.

[0012] Preferably, the polyglycerol mentioned in step (1) is selected from at least one of tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, and octaglycerol. The aforementioned polyglycerol has 6-10 reactive hydroxyl groups and a low molecular weight, enabling it to react and yield modified polyurethane acrylates with multifunctional photocurable reactive groups, while ensuring good crosslinking density. This improves both photocuring efficiency and the strength of the cured product. Furthermore, the flexible polyether backbone of the polyglycerol can improve the toughness of the cured product.

[0013] Preferably, the diisocyanate compound in step (1) is selected from linear hexamethylene diisocyanate. This invention significantly improves the interfacial adhesion of UV adhesives by introducing a high content of highly polar urethane groups through the reaction of a diisocyanate compound with hydroxyl groups. Furthermore, the urethane groups formed by using a linear diisocyanate compound and polyglycerol offer greater freedom of choice and have a more significant effect on improving adhesion.

[0014] Preferably, the ratio of polyglycerol to diisocyanate compound in step (1) is controlled according to a molar ratio of hydroxyl to isocyanate groups of 1:1.5-2. An isocyanate-terminated intermediate is obtained by using an excess of isocyanate groups.

[0015] Preferably, the catalyst in step (1) is dibutyltin dilaurate, stannous octoate, or dibutyltin diacetate, the anhydrous diluent is N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF), the heating reaction temperature is 50-80°C, and the reaction time is 2-5 h.

[0016] Preferably, the hydroxy methacrylate in step (2) is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate, and the molar ratio of the amount of hydroxy methacrylate added to the diisocyanate compound is 0.8-1.2:1.

[0017] Preferably, the reactive diluent monomer in step (3) is one or more of the following: methyl methacrylate, ethyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, isobornyl methacrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate.

[0018] Preferably, the photoinitiator in step (3) is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (photoinitiator TPO), 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide (photoinitiator TMO), or ethyl 2,4,6-trimethylbenzoylphenylphosphonate (photoinitiator TPO-L).

[0019] Preferably, the vinyl MQ silicone resin in step (3) is a vinyl MQ silicone resin with a vinyl content of 1-5wt% and a viscosity of 10000-20000mPa·s.

[0020] This invention uses vinyl MQ silicone resin as a filler, which can participate in the UV curing crosslinking reaction, significantly improving wear resistance, and has a low impact on the adhesion of the cured film.

[0021] Preferably, the weight ratio of each material in step (3) is as follows: 100 parts of modified polyurethane acrylate, 100-200 parts of reactive diluent monomer, 2-15 parts of vinyl MQ silicone resin, and 1-15 parts of photoinitiator.

[0022] The chemical principle involved in the preparation method of this invention is as follows: First, a first-step urethane esterification reaction is carried out between polyglycerol and a diisocyanate compound to obtain an isocyanate-terminated oligomer with a multi-branched structure. Then, a second-step urethane esterification reaction is carried out with (meth)acrylate hydroxyl ester, grafting photocurable crosslinkable (meth)acrylate groups onto the terminal isocyanate groups to obtain a modified polyurethane acrylate with multifunctional photocurable reactive groups. The above-mentioned modified polyurethane acrylate has a flexible polyether backbone and multiple crosslinking active sites, which significantly improves the photocuring efficiency while simultaneously improving the strength and toughness of the cured product. Furthermore, the high content and high polarity of urethane groups formed by the urethane esterification reaction can significantly improve the adhesion of the UV adhesive interface. By further combining vinyl MQ silicone resin as a reinforcing filler, it can participate in the UV curing crosslinking reaction, has good compatibility with the cured film, and significantly improves the wear resistance while having a low impact on the adhesion of the cured film.

[0023] A high-adhesion, abrasion-resistant UV adhesive prepared by the above method.

[0024] The application of the above-mentioned high-adhesion, abrasion-resistant UV adhesive in artificial nails.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] (1) The present invention uses a specific modified polyurethane acrylate to modify the acrylic resin UV adhesive, which can significantly improve the adhesion, strength, toughness and light curing efficiency of the obtained UV adhesive.

[0027] (2) The present invention uses vinyl MQ silicone resin as a reinforcing filler, which can significantly improve wear resistance and avoid the reduction in adhesion and toughness caused by conventional fillers. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0029] Example 1

[0030] A method for preparing a high-adhesion, abrasion-resistant UV adhesive includes the following preparation steps:

[0031] (1) Tetraglyceride, hexamethylene diisocyanate, dibutyltin dilaurate catalyst and NMP solvent were added to a reaction vessel and stirred until homogeneous. The amount of tetraglyceride and hexamethylene diisocyanate added was controlled so that the molar ratio of hydroxyl to isocyanate groups was 1:1.5. Then the mixture was heated to 50°C and stirred for 5 h until the hydroxyl value of the product was <5 mg KOH / g, thus obtaining an isocyanate-terminated oligomer solution.

[0032] (2) Hydroxyethyl methacrylate was added to the oligomer solution in step (1) and the reaction was continued at a constant temperature. The molar ratio of the amount of hydroxyethyl methacrylate added to hexamethylene diisocyanate was 0.8:1. After the reaction was completed, the isocyanate group content of the product was measured to be <1wt%. After the reaction was completed, the solvent was removed under reduced pressure to obtain modified polyurethane acrylate.

[0033] (3) Take 100 parts by weight of the modified polyurethane acrylate obtained in step (2) and mix it evenly with 50 parts by weight of hydroxyethyl methacrylate, 30 parts by weight of isobornyl methacrylate, 20 parts by weight of ethyl methacrylate, 5 parts by weight of vinyl MQ silicone resin with a vinyl content of 2wt% and a viscosity of 15000mPa·s and 6 parts by weight of photoinitiator TMO to obtain a high-adhesion wear-resistant UV adhesive.

[0034] The application performance test of the high-adhesion, abrasion-resistant UV adhesive obtained in this embodiment, used to prepare artificial nails via UV curing, is as follows:

[0035] 1. The curing time was measured by irradiating the surface of a glass slide with the pre-coated resin composition using a 370nm UV-LED lamp and testing it using the touch method. The result was 9 seconds.

[0036] 2. Adhesion was tested according to GB / T 9286-2021. The test result was grade 0.

[0037] 3. Abrasion resistance was tested according to GB / T1768-2006, with a load of 1.0 kg. The test result was 148 cycles.

[0038] 4. Shear strength was tested according to GB / T 7124-2008. The test result was 24.5 MPa.

[0039] 5. Elongation at break was tested according to ASTM D882. The result was 40.7%.

[0040] Example 2

[0041] A method for preparing a high-adhesion, abrasion-resistant UV adhesive includes the following preparation steps:

[0042] (1) Hexaglycerol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst and NMP solvent were added to a reaction vessel and stirred until homogeneous. The amount of hexaglycerol and hexamethylene diisocyanate added was controlled so that the molar ratio of hydroxyl to isocyanate groups was 1:1.7. Then the mixture was heated to 60°C and stirred for 4 hours until the hydroxyl value of the product was <5 mgKOH / g, thus obtaining an isocyanate-terminated oligomer solution.

[0043] (2) Hydroxypropyl methacrylate was added to the oligomer solution in step (1) and the reaction was continued at a constant temperature. The molar ratio of the amount of hydroxypropyl methacrylate added to hexamethylene diisocyanate was 1:1. After the reaction was completed, the isocyanate group content of the product was measured to be <1wt%. After the reaction was completed, the solvent was removed under reduced pressure to obtain modified polyurethane acrylate.

[0044] (3) Take 100 parts by weight of the modified polyurethane acrylate obtained in step (2) and mix it evenly with 80 parts by weight of hydroxypropyl methacrylate, 30 parts by weight of isoborneol methacrylate, 40 parts by weight of ethyl methacrylate, 10 parts by weight of vinyl MQ silicone resin with a vinyl content of 2wt% and a viscosity of 15000mPa·s and 8 parts by weight of photoinitiator TMO to obtain a high-adhesion wear-resistant UV adhesive.

[0045] The high-adhesion abrasion-resistant UV adhesive obtained in this embodiment was tested and cured in 7 seconds. The adhesion test result was 0, the abrasion resistance test result was 170 cycles, the shear strength test result was 27.2 MPa, and the elongation at break test result was 37.6%.

[0046] Example 3

[0047] A method for preparing a high-adhesion, abrasion-resistant UV adhesive includes the following preparation steps:

[0048] (1) Octameric glycerol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst and NMP solvent were added to a reaction vessel and stirred until homogeneous. The amount of octameric glycerol and hexamethylene diisocyanate added was controlled so that the molar ratio of hydroxyl groups to isocyanate groups was 1:2. Then the mixture was heated to 70°C and stirred for 3 hours until the hydroxyl value of the product was <5 mgKOH / g, thus obtaining an isocyanate-terminated oligomer solution.

[0049] (2) Hydroxybutyl methacrylate was added to the oligomer solution in step (1) and the reaction was continued at a constant temperature. The molar ratio of the amount of hydroxybutyl methacrylate added to hexamethylene diisocyanate was 1.2:1. After the reaction was completed, the isocyanate group content of the product was measured to be <1wt%. After the reaction was completed, the solvent was removed under reduced pressure to obtain modified polyurethane acrylate.

[0050] (3) Take 100 parts by weight of the modified polyurethane acrylate obtained in step (2) and mix it evenly with 120 parts by weight of hydroxybutyl methacrylate, 30 parts by weight of isobornyl methacrylate, 50 parts by weight of ethyl methacrylate, 15 parts by weight of vinyl MQ silicone resin with a vinyl content of 2wt% and a viscosity of 15000mPa·s and 10 parts by weight of photoinitiator TMO to obtain a high-adhesion wear-resistant UV adhesive.

[0051] The high-adhesion abrasion-resistant UV adhesive obtained in this embodiment was tested and cured in 6 seconds. The adhesion test result was 0, the abrasion resistance test result was 185 times, the shear strength test result was 28.7 MPa, and the elongation at break test result was 34.4%.

[0052] Example 4

[0053] A method for preparing a high-adhesion, abrasion-resistant UV adhesive includes the following preparation steps:

[0054] (1) Hexaglycerol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst and DMF solvent were added to a reaction vessel and stirred until homogeneous. The amount of hexaglycerol and hexamethylene diisocyanate added was controlled so that the molar ratio of hydroxyl groups to isocyanate groups was 1:2. Then the mixture was heated to 80°C and stirred for 2 hours until the hydroxyl value of the product was <5 mgKOH / g, thus obtaining an isocyanate-terminated oligomer solution.

[0055] (2) Hydroxyethyl methacrylate was added to the oligomer solution in step (1) and the reaction was continued at a constant temperature. The molar ratio of the amount of hydroxyethyl methacrylate added to hexamethylene diisocyanate was 1:1. After the reaction was completed, the isocyanate group content of the product was measured to be <1wt%. After the reaction was completed, the solvent was removed under reduced pressure to obtain modified polyurethane acrylate.

[0056] (3) Take 100 parts by weight of the modified polyurethane acrylate obtained in step (2) and mix it evenly with 70 parts by weight of hydroxyethyl methacrylate, 50 parts by weight of isobornyl methacrylate, 50 parts by weight of ethyl methacrylate, 12 parts by weight of vinyl MQ silicone resin with a vinyl content of 2wt% and a viscosity of 15000mPa·s and 10 parts by weight of photoinitiator TPO-L to obtain a high-adhesion wear-resistant UV adhesive.

[0057] The high-adhesion abrasion-resistant UV adhesive obtained in this embodiment was tested and cured in 6 seconds. The adhesion test result was 0, the abrasion resistance test result was 181 times, the shear strength test result was 28.3 MPa, and the elongation at break test result was 35.0%.

[0058] Example 5

[0059] In this embodiment, toluene diisocyanate is used instead of hexamethylene diisocyanate in Example 1, and the rest are the same.

[0060] The UV adhesive obtained in this embodiment was tested and found to have a curing time of 9 seconds, an adhesion test result of level 1, an abrasion resistance test result of 151 cycles, a shear strength test result of 25.2 MPa, and an elongation at break test result of 34.5%.

[0061] The comparison between Example 5 and Example 1 shows that the UV adhesive obtained by using linear hexamethylene diisocyanate in this invention has better adhesion and toughness than toluene diisocyanate containing a cyclic structure.

[0062] Comparative Example 1

[0063] In this comparative example, a commercially available conventional UV-curable 6-functional polyurethane acrylate (Jining Tangyi Chemical Co., Ltd., 6-functional polyurethane modified acrylate R2601) was used instead of the modified polyurethane acrylate in Example 1, and the rest were the same.

[0064] The UV adhesive obtained in this comparative example was tested and found to have a curing time of 15s, an adhesion test result of level 1, an abrasion resistance test result of 145 cycles, a shear strength test result of 24.8MPa, and an elongation at break test result of 28.1%.

[0065] The comparison results between Comparative Example 1 and Example 1 show that the modified polyurethane acrylate with polyglycerol backbone of the present invention can significantly improve the photocuring efficiency and the adhesion and toughness of the cured product compared with conventional polyurethane acrylate.

[0066] Comparative Example 2

[0067] This comparative example uses nano-silica filler instead of the vinyl MQ silicone resin in Example 1, and the rest are the same.

[0068] The UV adhesive obtained in this comparative example was tested and found to have a curing time of 12s, an adhesion test result of level 1, an abrasion resistance test result of 150 cycles, a shear strength test result of 21.6MPa, and an elongation at break test result of 30.7%.

[0069] The comparison results between Comparative Example 2 and Example 1 show that the vinyl MQ silicone resin used in this invention can significantly improve the photocuring efficiency and the adhesion, strength and toughness of the cured product compared with conventional silica fillers.

[0070] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a high-adhesion, abrasion-resistant UV adhesive, characterized in that: The preparation steps include the following: (1) Polyglycerol and diisocyanate compound were heated and reacted under the conditions of catalyst and anhydrous diluent to obtain an isocyanate-terminated oligomer solution; (2) Add (meth)acrylate hydroxy ester to the oligomer solution in step (1) and continue the reaction. After the reaction is completed, remove the solvent to obtain modified polyurethane acrylate. (3) The modified polyurethane acrylate obtained in step (2) is mixed evenly with reactive diluent monomer, vinyl MQ silicone resin and photoinitiator to obtain a high-adhesion wear-resistant UV adhesive.

2. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The polyglycerol mentioned in step (1) is selected from at least one of tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, and octaglycerol, and the diisocyanate compound is selected from linear hexamethylene diisocyanate.

3. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 2, characterized in that: The ratio of polyglycerol to diisocyanate compound is controlled according to a molar ratio of hydroxyl to isocyanate group of 1:1.5-2.

4. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The catalyst in step (1) is dibutyltin dilaurate, stannous octoate, or dibutyltin diacetate, the anhydrous diluent is N-methylpyrrolidone or N,N-dimethylformamide, the heating reaction temperature is 50-80℃, and the reaction time is 2-5h.

5. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The hydroxy methacrylate mentioned in step (2) is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate, and the molar ratio of the amount of hydroxy methacrylate added to the diisocyanate compound is 0.8-1.2:

1.

6. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The reactive diluent monomer mentioned in step (3) is one or more of methyl methacrylate, ethyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, isobornyl methacrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, or ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

7. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The vinyl MQ silicone resin mentioned in step (3) is a vinyl MQ silicone resin with a vinyl content of 1-5wt% and a viscosity of 10000-20000mPa·s.

8. The method for preparing a high-adhesion, abrasion-resistant UV adhesive according to claim 1, characterized in that: The weight ratio of each material in step (3) is as follows: 100 parts of modified polyurethane acrylate, 100-200 parts of reactive diluent monomer, 2-15 parts of vinyl MQ silicone resin, and 1-15 parts of photoinitiator.

9. A high-adhesion, abrasion-resistant UV adhesive prepared by the method described in any one of claims 1-8.

10. The application of the high-adhesion, abrasion-resistant UV adhesive as described in claim 9 in artificial nails.