A high-ductility and high-hardness thin film coating composition, coating and manufacturing method thereof

Abstract

The present invention relates to the technical field of radiation-cured materials, and in particular to a high-ductility and high-hardness thin-film coating composition, coating, and preparation method thereof for automobile invisible car cover film. The coating composition comprises the following raw materials in parts by weight: 100 parts of high-ductility radiation-cured resin, 5-15 parts of thermoplastic solid acrylic resin, 1-5 parts of antioxidant, 20-50 parts of photopolymerizable monomer, 2-10 parts of photoinitiator, 5-20 parts of epoxy resin, and 0.05-0.5 parts of amine catalyst. The high-ductility and high-hardness thin-film coating composition and the preparation method of the coating provided in the present application have both high ductility (more than 300%) and high hardness (3H), and will not turn yellow at high temperatures, and are suitable for the field of functional films, particularly for automobile invisible car cover films. The preparation method of the coating is simple, there is no VOC emission during the preparation process, which avoids pollution to the environment, and also reduces operational risks, with significant environmental advantages.

Description

Technical Field

[0001] The present invention relates to the technical field of radiation-cured materials, and in particular to a high-ductility and high-hardness thin film coating for automobile invisible car cover film and a preparation method thereof. Background Art

[0002] TPU invisible car film is a new, high-performance, environmentally friendly film, also known as transparent paint protection film. It possesses exceptional toughness, insulating the car's paint from air, maintaining a long-lasting high gloss. The film also self-heals from scratches, providing long-lasting protection.

[0003] TPU invisible car cover features a self-healing scratch feature, achieved through the use of TPU material and a special surface coating. TPU, short for thermoplastic polyurethane elastomer rubber, is a material with exceptional elasticity and memory recovery (the film itself has an ductility of nearly 300%). Therefore, even if a TPU-based invisible car cover ruptures due to external forces such as stretching, it will slowly return to its original shape once the force is removed. The TPU film coating primarily provides protection, making the cover less susceptible to wear and tear, and more durable.

[0004] Hardness and ductility are both important performance indicators for TPU film coatings. If the hardness of the film coating does not meet the required level, it is prone to scratch damage; if the ductility does not meet the required level, it can cause abnormalities such as white fog, cracking, and even breakage. Currently, TPU film coatings generally use solvent-based thermosetting polyurethane resin systems. The production process generates VOC emissions, and the solvent can penetrate the TPU substrate to a certain extent, resulting in a decrease in overall strength. It is also difficult to achieve a ductility of 300% while maintaining a high hardness (3H) on the coating surface.

[0005] Therefore, it is necessary to develop a thin film coating that has both high ductility and high hardness. Summary of the Invention

[0006] In response to the above-mentioned problems existing in the prior art, the applicant of the present invention provides a high-ductility and high-hardness thin film coating composition and a method for manufacturing the same.

[0007] The high-ductility and high-hardness thin-film coating composition of the present invention adopts solvent-free radiation curing technology and has no VOC emissions. The formed cured film has both high ductility (300%) and high hardness (3H), and does not yellow at high temperatures. It can be used in the fields of automotive cover films and functional films.

[0008] A first aspect of the present application is to provide a high-ductility and high-hardness thin film coating composition.

[0009] The specific technical solutions are as follows:

[0010] A high-ductility and high-hardness thin film coating composition comprises the following raw materials in parts by weight:

[0011] 100 parts of high ductility radiation curing resin;

[0012] 5-15 parts of thermoplastic solid acrylic resin;

[0013] 1-5 parts of antioxidant;

[0014] 20-50 parts of photopolymerizable monomer;

[0015] 2-10 parts of photoinitiator;

[0016] 5-20 parts of epoxy resin;

[0017] 0.05-0.5 parts of amine catalyst.

[0018] Furthermore, the high-ductility radiation-curable resin is a polyurethane acrylate resin;

[0019] Furthermore, the high-ductility radiation-curable resin is an aliphatic polyurethane acrylate resin or an alicyclic polyurethane acrylate resin.

[0020] Furthermore, the high-ductility radiation-curable resin has a ductility of 200%-600%;

[0021] Furthermore, the high ductility radiation-curable resin has a ductility of 200%-300%, 300%-400%, 400%-500%, 500%-600%;

[0022] Furthermore, the high ductility radiation-curable resin has a ductility of 300%-400%, 400%-500%;

[0023] When the ductility of the polyurethane acrylate resin itself is low, such as below 200%, some corners will need to be stretched vigorously during the actual film application process, which can easily lead to abnormalities such as white fog, cracking, and even breakage. When the ductility of the polyurethane acrylate resin itself is high, such as above 600%, the hardness of the film coating will not meet the requirements, and scratch damage may occur.

[0024] In some embodiments, the high-ductility radiation-curable resin is an aromatic polyurethane acrylate resin. In this case, the prepared film is prone to yellowing abnormality at high temperatures.

[0025] In some embodiments, the high ductility radiation-curable resin is selected from one or more of CN8881 NS, CN8887 NS, and CN8888 NS produced by Sartomer; 61329, 61362, 61365, 61369, DR-U384, and DR-U388 produced by Changxing;

[0026] Furthermore, the Tg (glass transition temperature) of the thermoplastic solid acrylic resin is 30°C to 90°C;

[0027] Furthermore, the Tg of the thermoplastic solid acrylic resin is 50°C to 70°C.

[0028] In some embodiments, the thermoplastic solid acrylic resin is selected from one or more of DSM Neoresins B-817, B-736, B-814, B-805, B-735, B-725, B-801, and B-810.

[0029] When the Tg of the thermoplastic solid acrylic resin is lower than 30°C, the hardness of the film coating is low and the scratch resistance is poor, which can easily cause scratch damage during use; when the Tg is greater than 90°C, the film coating will crack abnormally when stretched.

[0030] Furthermore, the antioxidant has a structure of formula I

[0031]

[0032] Formula I

[0033] Wherein, R1 and R2 are independently H, methyl, ethyl, n-propyl, isopropyl, or n-butyl.

[0034] When the antioxidant uses the structure of formula I, it is different from the antioxidant with a fully hindered phenol structure (such as BASF IRGANOX1010). The antioxidant with the structure of formula I has a tert-butyl group and a semi-hindered phenol structure at the phenolic hydroxyl position, which is sufficient to provide protection for itself. At the same time, since the steric hindrance of the hindered phenolic hydroxyl group is weakened to a certain extent, the yellowing resistance requirement is met; at the same time, the linear chain segment structure is conducive to improving the flexibility of the system and avoiding abnormalities such as white fog, cracking and breakage of the film coating during stretching.

[0035] In some embodiments, the antioxidant is selected from one or more of IRGANOX AO 30, IRGANOX AO 40, IRGANOX AO 50, IRGANOX AO 60, IRGANOX AO 70, IRGANOX AO 80, and IRGANOX AO 90 produced by BASF; STAB AO 30, STAB AO 40, STABAO 50, STAB AO 60, STAB AO 70, STAB AO80, and STAB AO 90 produced by ADEKA; and GA70, GA80, and GA90 produced by Sumitomo Chemical.

[0036] In some preferred embodiments, the antioxidant is selected from at least one of IRGANOX AO 80, STAB AO 80, and GA80; the use of these preferred antioxidants can better balance the yellowing resistance and dispersibility.

[0037] Furthermore, the photopolymerizable monomer is selected from 1,4-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated di(meth)acrylate, One or more of cyclohexyl ester, isocyanurate, di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0038] Further, the photoinitiator is selected from acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bis(dimethylamino)benzophenone, benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5- Diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-phenylvinyl-1,3,-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4, 6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5- dimethoxyphenyl)-4,6-bis(dichloromethyl)-1,3,5-triazine, 2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halogenated methyl-s-triazines, 2-(o-benzoyloxime)-1- [4-(Phenylthio)phenyl]-1,2-butanedione, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-hexanedione, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2- One or more of butanedione, 2-(o-benzoyloxime)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide.

[0039] Further, the amine catalyst is selected from triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethyl-bis(2-aminoethyl)ether, N,N-dimethylhexanolamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetriamine, N-(2-hydroxypropyl)-N,N',N"N"-tetramethyldiethylenetriamine, N,N, N'-trimethyl-N'-(2-hydroxyethyl)propylenediamine, N-methyl-N'-(2-hydroxyethyl)piperazine, bis(N,N-dimethylaminopropyl)amine, bis(N,N-dimethylaminopropyl)isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidine, 3-quinuclidine, 4-quinuclidine, 1-(2'-hydroxypropyl)imidazole, 1-(2'-hydroxypropyl)-2-methylimidazole, 1-(2'-hydroxyethyl)imidazole, 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxypropyl)-2-methylimidazole, 1-(3'-aminopropyl)imidazole, 1-(3'-aminopropyl)-2-methylimidazole, 1-(3'-hydroxypropyl)imidazole, 1-(3'-hydroxypropyl)-2-methylimidazole, N,N- One or more of dimethylaminopropyl-N'-(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N'N'-bis(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N'N'-bis(2-hydroxypropyl)amine, N,N-dimethylaminoethyl-N',N'-bis(2-hydroxyethyl)amine, 2-ethyl-4-methylimidazole, 2-methylimidazole, N,N-dimethylaminoethyl-N'N'-bis(2-hydroxypropyl)amine, melamine, and benzoguanamine.

[0040] In some preferred embodiments, the amine catalyst is selected from at least one of 2-ethyl-4-methylimidazole and 2-methylimidazole.

[0041] Furthermore, the epoxy resin is selected from bisphenol A epoxy resin, epoxide of resin obtained by condensation reaction of bisphenol A and formaldehyde, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butylphenol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl parahydroxybenzoic acid, diglycidyl diol, tetraglycidyl diaminodiphenylmethane, triglycidyl One or more of p-aminophenol, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyl tris(2-hydroxyethyl)isocyanurate, and dicyclopentadiene-type epoxy resin.

[0042] The second aspect of the present application is to provide a method for preparing a high-ductility and high-hardness thin-film coating composition, the preparation method comprising the following steps:

[0043] S11: 100 parts of a high-ductility radiation-curable resin, 0-15 parts of a thermoplastic solid acrylic resin, 1-5 parts of an antioxidant, and 20-50 parts of a photopolymerizable monomer are mixed and uniformly dispersed;

[0044] S12: Add 2-10 parts of photoinitiator while stirring to ensure uniform dispersion;

[0045] S13: adding 5-20 parts of epoxy resin and 0.05-0.5 parts of amine catalyst, stirring and dispersing them uniformly; and obtaining the high-ductility and high-hardness thin film coating composition.

[0046] Furthermore, the dispersion method uses a disperser;

[0047] Furthermore, in step S11, the speed of the disperser is 1000-3000 rpm, and the dispersion time is 20-40 minutes;

[0048] Furthermore, in step S12, the speed of the disperser is 1000-3000 rpm, and the dispersion time is 10-30 minutes;

[0049] Furthermore, in step S13, the speed of the disperser is 800-1500 rpm, and the dispersion time is 10-30 minutes;

[0050] The third aspect of the present application is to provide a method for preparing a high-ductility and high-hardness thin film coating, the preparation method comprising the following steps:

[0051] S21: first, a high-ductility and high-hardness thin film coating composition is applied to a TPU substrate using a wire rod to form a liquid coating having a thickness of 20 to 40 μm;

[0052] S22: The TPU substrate containing the liquid coating is then passed through a UV curing device for radiation curing using a conveyor belt;

[0053] S23: Curing in an oven at a high temperature of 80 to 150 degrees for 30 to 90 minutes to prepare a high-ductility and high-hardness thin film coating.

[0054] In one embodiment, the light source for UV curing is an electrodeless lamp or a mercury lamp;

[0055] Furthermore, the electrodeless lamp model is Heraeus F300, with a power density of 200~400w / in;

[0056] Furthermore, the cumulative light dose of the electrodeless lamp reaches 500~2000mJ / cm2.

[0057] The fourth aspect of the present application is to provide an application of a thin film coating composition, which is characterized in that it forms a dry film and a cured product through photocuring and thermal curing, and is used to prepare automobile invisible car cover films and functional films.

[0058] Beneficial effects:

[0059] The beneficial effects of this application are:

[0060] The cured film prepared by the high-ductility and high-hardness thin-film coating composition and preparation method provided in this application has both high ductility (more than 300%) and high hardness (3H), and does not yellow at high temperatures. It is suitable for the field of functional films, especially for automotive invisible car cover films.

[0061] The present application also provides a method for preparing a high-ductility and high-hardness thin film coating. The preparation method is simple, and there is no VOC emission during the preparation process, which avoids pollution to the environment and reduces operational risks, thus having significant environmental advantages. DETAILED DESCRIPTION

[0062] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0063] Performance testing method:

[0064] (1) Ductility test

[0065] Use a long strip specimen with a width of (25 ± 0.1) mm and a length of at least 250 mm. The clamp spacing is 100 mm, the specimen gauge length is 50 mm, the tensile speed is (300 ± 10) mm / min, and when the tensile length is 300%, observe the film coating with the naked eye to see if there are any abnormalities such as white fog, cracks or breaks, and record the observation phenomenon.

[0066] (2) Hardness test

[0067] Fix the sample to be tested face up on the table, sharpen the pencil with fine sandpaper, and make a 45° angle with the plane of the coating. Let the pencil make a plow-like stroke on the coating. Change a pencil each time and keep the same pressure and 45° angle. Start with the hardest pencil and test from hard to soft one by one until you find a pencil that does not scratch the coating. The hardness of this pencil is the hardness of the coating being tested.

[0068] (3) High temperature yellowing resistance test

[0069] After the test sample is placed in a 70-degree oven for 168 hours, the b1 and b2 before and after the oven are measured using InterLab ColorQuest XE. The △E value is the difference between b2-b1. The larger the value, the more serious the yellowing.

[0070] The present invention is described in detail below. The raw materials and amounts of the raw materials used in each example are shown in Table 1.

[0071] Table 1 Allocation ratio of each group in the embodiment

[0072]

[0073] Example 1

[0074] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0075] First, 100 parts of a high-ductility radiation-curable resin (CN8881 NS, ductility 346% produced by Sartomer), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64°C), 3 parts of an antioxidant (IRGANOX AO 80, produced by BASF), and 35 parts of a photopolymerizable monomer (EM265, produced by Changxing Chemical) were mixed and dispersed in a disperser at 1000 rpm for 30 minutes.

[0076] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 3000 rpm for 15 minutes;

[0077] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000, 6 parts of Nan Ya NPEF170) and 0.2 parts of amine catalyst (2E4MZ from Shikoku Chemical Co., Ltd.) were added, and the mixture was stirred and dispersed at a speed of 1000 rpm for 20 minutes to prepare the high ductility and high hardness thin film coating composition.

[0078] The preparation of a high-ductility and high-hardness thin film coating comprises the following steps:

[0079] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0080] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0081] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0082] Example 2

[0083] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0084] First, 100 parts of a high-ductility radiation-curable resin (CN8881 NS, ductility 346% produced by Sartomer), 5 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64°C), 5 parts of an antioxidant (IRGANOX AO 80, produced by BASF), and 20 parts of a photopolymerizable monomer (EM265, produced by Changxing Chemical) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0085] Then add 5 parts of photoinitiator (4.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 1000 rpm for 25 minutes;

[0086] Then, 20 parts of epoxy resin (10 parts of Nippon Kayaku NC3000, 10 parts of Nanya NPEF170) and 0.5 parts of amine catalyst (2E4MZ from Shikoku Chemical Co., Ltd.) were added, and the mixture was stirred and dispersed at a speed of 1500 rpm for 20 minutes to prepare the high ductility and high hardness thin film coating composition.

[0087] The preparation of a high-ductility and high-hardness thin film coating comprises the following steps:

[0088] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0089] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0090] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0091] Example 3

[0092] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0093] First, 100 parts of a high-ductility radiation-curable resin (CN8881 NS, ductility 346% produced by Sartomer), 15 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64°C), 2 parts of an antioxidant (IRGANOX AO 80, produced by BASF), and 50 parts of a photopolymerizable monomer (EM265, produced by Changxing Chemical) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0094] Then add 8 parts of photoinitiator (7.3 parts of Irgacure 907 produced by Ciba, 0.7 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0095] Then, 5 parts of epoxy resin (2.5 parts of Nippon Kayaku NC3000, 2.5 parts of Nanya NPEF170) and 0.05 parts of amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at a speed of 1000 rpm for 20 minutes to prepare the high ductility and high hardness thin film coating composition.

[0096] The preparation of a high-ductility and high-hardness thin film coating comprises the following steps:

[0097] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0098] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0099] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0100] Example 4

[0101] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0102] First, 100 parts of a high-ductility radiation-curable resin (61365 produced by Changxing, ductility 488%), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64 degrees), 3 parts of an antioxidant (BASF IRGANOX AO80), and 35 parts of a photopolymerizable monomer (Changxing Chemical EM265) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0103] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0104] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000 and 6 parts of Nanya NPEF170) and 0.2 parts of an amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at 1000 rpm for 20 minutes to produce the high-ductility, high-hardness thin film coating composition.

[0105] A method for preparing a high-ductility and high-hardness thin film coating, characterized in that the preparation method comprises the following steps:

[0106] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0107] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0108] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0109] Example 5

[0110] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0111] First, 100 parts of a high-ductility radiation-curable resin (DR-U388 produced by Changxing, ductility 373%), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64 degrees), 3 parts of an antioxidant (BASF IRGANOX AO80), and 35 parts of a photopolymerizable monomer (Changxing Chemical EM265) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0112] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0113] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000 and 6 parts of Nanya NPEF170) and 0.2 parts of an amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at 1000 rpm for 20 minutes to produce the high-ductility, high-hardness thin film coating composition.

[0114] A method for preparing a high-ductility and high-hardness thin film coating, characterized in that the preparation method comprises the following steps:

[0115] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0116] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0117] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0118] Comparative Example 1

[0119] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0120] First, 100 parts of a high-ductility radiation-curable resin (CN8888 NS, ductility 963% produced by Sartomer), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64°C), 3 parts of an antioxidant (BASF IRGANOXAO 80), and 35 parts of a photopolymerizable monomer (Evergreen Chemical EM265) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0121] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0122] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000 and 6 parts of Nanya NPEF170) and 0.2 parts of an amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at 1000 rpm for 20 minutes to produce the high-ductility, high-hardness thin film coating composition.

[0123] A method for preparing a high-ductility and high-hardness thin film coating, characterized in that the preparation method comprises the following steps:

[0124] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0125] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0126] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0127] Comparative Example 2

[0128] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0129] First, 100 parts of a high-ductility radiation-curable resin (CN8881 NS, ductility 346% produced by Sartomer), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-811, Tg 110 degrees), 3 parts of an antioxidant (BASF IRGANOX AO 80), and 35 parts of a photopolymerizable monomer (Evergreen Chemical EM265) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0130] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0131] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000 and 6 parts of Nanya NPEF170) and 0.2 parts of an amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at 1000 rpm for 20 minutes to produce the high-ductility, high-hardness thin film coating composition.

[0132] A method for preparing a high-ductility and high-hardness thin film coating, characterized in that the preparation method comprises the following steps:

[0133] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0134] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0135] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0136] Comparative Example 3

[0137] A method for preparing a high-ductility and high-hardness thin-film coating composition, comprising the following steps:

[0138] First, 100 parts of a high-ductility radiation-curable resin (CN8881 NS produced by Sartomer, ductility 346%), 10 parts of a thermoplastic solid acrylic resin (DSM Neoresin B-817, Tg 64°C), 3 parts of an antioxidant (BASF IRGANOX 1010), and 35 parts of a photopolymerizable monomer (Evergreen Chemical EM265) were mixed and dispersed in a disperser at 2000 rpm for 30 minutes.

[0139] Then add 6 parts of photoinitiator (5.5 parts of Irgacure 907 produced by Ciba, 0.5 parts of Irgacure OXE02 produced by Ciba) while stirring, and stir and disperse at a speed of 2000 rpm for 15 minutes;

[0140] Then, 12 parts of epoxy resin (6 parts of Nippon Kayaku NC3000 and 6 parts of Nanya NPEF170) and 0.2 parts of an amine catalyst (2E4MZ from Shikoku Chemical) were added, and the mixture was stirred and dispersed at 1000 rpm for 20 minutes to produce the high-ductility, high-hardness thin film coating composition.

[0141] A method for preparing a high-ductility and high-hardness thin film coating, characterized in that the preparation method comprises the following steps:

[0142] (1) First, a high-ductility and high-hardness thin film coating composition is coated on a TPU substrate using a wire rod to form a liquid coating with a thickness of 30 μm;

[0143] (2) The TPU substrate containing the liquid coating was then passed through a UV curing device (electrodeless lamp, Heraeus F300, power density 300w / in) using a conveyor belt for radiation curing, with a cumulative light dose of 1000mJ / cm2;

[0144] (3) The film was then cured in a high-temperature oven at 120 degrees for 60 minutes to prepare a high-ductility and high-hardness thin film coating.

[0145] Performance test results:

[0146] The high-ductility and high-hardness thin film coatings obtained in Examples 1 to 3 of the present invention and Comparative Examples 1 to 3 were subjected to ductility tests, hardness tests, and high-temperature yellowing resistance tests. The test results are shown in Table 2.

[0147] Table 2

[0148]

[0149] From the test results in Table 2, we can see that:

[0150] The thin film coatings prepared in Examples 1 to 5 have the characteristics of high ductility, high hardness, and high-temperature yellowing resistance, which are beneficial to the film lamination process and extend its service life; and the preparation process has no VOC emissions, is energy-saving and environmentally friendly.

[0151] The thin film coating prepared in Comparative Example 1 has high ductility but low hardness, resulting in reduced scratch resistance during use. This is because the use of a radiation-curable resin with a ductility exceeding 600% reduces the hardness of the final cured thin film coating, affecting the film's scratch resistance during normal use.

[0152] The thin film coating prepared in Comparative Example 2 has high hardness but low ductility, which affects normal film application. This is because the use of high-Tg thermoplastic solid acrylic resin results in a significant reduction in ductility, affecting the normal construction process and its service life.

[0153] The thin film coating prepared in Comparative Example 3 had substandard hardness and ductility, and poor yellowing resistance. This was due to the use of a conventional fully hindered phenol antioxidant, which resulted in poor ductility and yellowing resistance, affecting the normal construction process and service life.

[0154] Although the present invention has been disclosed above in terms of preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A high ductility and high hardness thin film coating composition, characterized in that: The raw materials include the following parts by weight: 100 parts of high ductility radiation curing resin, 5-15 parts of thermoplastic solid acrylic resin, 1-5 parts of antioxidants, 20-50 parts of photopolymerizable monomer, 2-10 parts of photoinitiator, 5-20 parts of epoxy resin, 0.05-0.5 parts of amine catalyst; The high-ductility radiation-curable resin is an aliphatic polyurethane acrylate resin or an alicyclic polyurethane acrylate resin having a ductility of 346%-600%; The thermoplastic solid acrylic resin has a glass transition temperature of 50°C-70°C; The antioxidant has the structure of formula I Wherein, R1 and R2 are independently H, methyl, ethyl, n-propyl, isopropyl, or n-butyl.

2. The method for preparing the high ductility and high hardness thin film coating composition according to claim 1, characterized in that The steps include: S11: 100 parts of a high-ductility radiation-curable resin, 5-15 parts of a thermoplastic solid acrylic resin, 1-5 parts of an antioxidant, and 20-50 parts of a photopolymerizable monomer are mixed and uniformly dispersed; S12: Add 2-10 parts of photoinitiator while stirring to ensure uniform dispersion; S13: adding 5-20 parts of epoxy resin and 0.05-0.5 parts of amine catalyst, stirring and dispersing them uniformly; and obtaining the high-ductility and high-hardness thin film coating composition.

3. A method for preparing a high-ductility and high-hardness thin film coating, characterized in that: A thin film coating composition according to claim 1 or a thin film coating composition prepared by the preparation method according to claim 2; The preparation method comprises the following steps: S21: first, a high-ductility and high-hardness thin film coating composition is applied to a TPU substrate using a wire rod to form a liquid coating having a thickness of 20 to 40 μm; S22: The TPU substrate containing the liquid coating is then passed through a UV curing device for radiation curing using a conveyor belt; S23: After curing in a high-temperature oven, a high-ductility and high-hardness thin film coating is obtained.

4. The method for preparing a high-ductility and high-hardness thin film coating according to claim 3, wherein: The light source in step S22 is an electrodeless lamp or a mercury lamp with a power density of 200-400w / in.

5. The method for preparing a high ductility and high hardness thin film coating according to claim 3, wherein: The curing temperature in step S23 is 80-150° C., and the curing time is 30-90 minutes.

6. The use of the thin film coating composition according to claim 1, or the thin film coating composition prepared by the preparation method according to claim 2, characterized in that: After light curing and heat curing, dry films and solids are formed, which are used to prepare automotive invisible car cover films and functional films.

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