CN114957607B - Photo-curing polyurethane acrylate prepolymer and hardened coating liquid - Google Patents
Photo-curing polyurethane acrylate prepolymer and hardened coating liquid Download PDFInfo
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- CN114957607B CN114957607B CN202210696878.8A CN202210696878A CN114957607B CN 114957607 B CN114957607 B CN 114957607B CN 202210696878 A CN202210696878 A CN 202210696878A CN 114957607 B CN114957607 B CN 114957607B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention relates to the technical field of light-cured resin, in particular to a light-cured urethane acrylate prepolymer and a hardened coating liquid. The prepolymer synthesis raw materials comprise: isocyanate, hydroxyl-terminated hyperbranched polyester, hydroxyl acrylate, fluorinated acrylate, a catalyst and a solvent; the hydroxyl number of the hydroxyl-terminated hyperbranched polyester is 4-24, the molecular weight is 600-4000, and the hydroxyl value is 300-520 mg KOH/g. The invention has the advantages of high toughness, high hardness and high wear resistance.
Description
Technical Field
The invention relates to the technical field of light-cured resin, in particular to a light-cured polyurethane acrylate prepolymer and a hardened coating liquid.
Background
With the continuous development and improvement of the curved screen technology, a flexible display product capable of being bent at will becomes an important development direction. The bottleneck of the current flexible display products is not in the display itself, but in the flexible cover plate. At present, a display part can be repeatedly bent for multiple times with a certain curvature, the daily requirement of a user can be met, the touch part of the display can also meet the requirement by using a thin film metal grid or a nano silver wire, but the daily requirement cannot be met by a flexible cover plate.
The flexible cover plate must have the characteristics of repeated bending, transparency, ultra-thinness, enough hardness and the like. It is not easy to find a material that has these properties at the same time. A conventional requirement for a flexible cover plate is to be able to bend more than 20 million times at a curvature of 10 mm diameter. In theory, glass with a thickness of less than 100 microns is possible to meet these characteristics, but there is still insufficient data support for bending performance. The development focus of solving the problem of flexible cover plates is currently achieved by colorless transparent polyimide (CPI) and a hardened coating.
Chinese patent application CN106896424A discloses a solvent-free uv-curing coating liquid, comprising the following components: 50-55 parts by weight of high official aliphatic urethane acrylate, 5-10 parts by weight of low official aliphatic urethane acrylate, 3-7 parts by weight of hydroxyethyl methacrylate, 1-3 parts by weight of 2 (2-ethoxy) ethyl acrylate, 5-9 parts by weight of a photocuring initiator and 0.05-0.2 part by weight of a surface auxiliary agent.
Chinese patent application CN103869387A discloses an ultraviolet light curing optical hardened film, which comprises a transparent substrate and an ultraviolet light curing hardened coating, wherein the hardened coating is formed by coating an ultraviolet light curing coating liquid on the transparent substrate and curing the ultraviolet light; the ultraviolet curing coating liquid consists of 30 to 70 weight parts of UV curing resin, 5 to 30 weight parts of reactive diluent, 2 to 10 weight parts of photoinitiator and 0.1 to 2 weight parts of auxiliary agent. The hardened coating has a surface roughness of less than or equal to 0.01 microns and the iridescence is substantially invisible.
Chinese patent application CN110358439A discloses a hardening liquid for a transparent polyimide hardening film, which comprises the following components in parts by weight: 50-80 parts of high-functionality polyurethane acrylate, 10-20 parts of multifunctional polyether acrylate, 10-20 parts of flexible monomer, 10-20 parts of reactive diluent, 0.5-2 parts of photoinitiator, 0.05-0.2 part of thermal initiator, 80-150 parts of good solvent, 2-20 parts of high-boiling-point poor solvent, 0.05-1 part of anti-fingerprint auxiliary agent and 10-30 parts of inorganic nano particles. According to the invention, the hardness of the hardened film is improved by adopting high-functionality polyurethane acrylate and multifunctional polyether acrylate, the toughness of the hardened film is improved by the flexible monomer, and meanwhile, the thermal initiator and the photoinitiator are added, and through the cooperation between thermal curing and photo-curing, the shrinkage stress generated by polymerization in the curing process is properly released, so that the generation of warping is avoided.
Chinese patent application CN113817437A discloses a hardening polyurethane acrylate adhesive and a preparation method thereof, a novel hardening adhesive formula is developed by utilizing a nano montmorillonite/UA branched substance preparation technology and combining superfine grinding, the technical problem of the trade-off of hardness and toughness of the existing hardening coating is solved, and a novel flexible display hardening coating material with excellent comprehensive performance is developed.
Therefore, the currently available hardened film has good hardness, wear resistance, or toughness, but it is difficult to have high toughness and good hardness and wear resistance.
Chinese patent application CN110734698A discloses a hardening coating liquid for a flexible cover plate, which is prepared by mixing a prepolymer with a hyperbranched structure, an active monomer and the like, the obtained hardening coating liquid is coated on a CPI film, and the CPI film can be used for the flexible cover plate through ultraviolet curing, has high toughness and high hardness and wear resistance, but the performances of the three aspects need to be further improved.
Therefore, it is necessary to develop a photocurable urethane acrylate prepolymer and a hardening coating solution that can solve the above-mentioned problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a photocuring urethane acrylate prepolymer and a hardening coating liquid which have the characteristics of high toughness, high hardness and high wear resistance.
The invention is realized by the following technical scheme:
a photo-curing urethane acrylate prepolymer is prepared from the following raw materials: isocyanate, hydroxyl-terminated hyperbranched polyester, hydroxyl acrylate, fluorinated acrylate, a catalyst and a solvent; the hydroxyl number of the hydroxyl-terminated hyperbranched polyester is 4-24, the molecular weight is 600-4000, and the hydroxyl value is 300-520 mg KOH/g.
In the present invention, "molecular weight" means weight average molecular weight unless otherwise specified.
Preferably, the isocyanate is an aliphatic diisocyanate.
Preferably, the hydroxyacrylate is a monofunctional monohydroxyacrylate.
Preferably, the fluorinated acrylate has a fluorine substitution number of 4 to 5 and a functionality of 2.
Preferably, the catalyst is dibutyltin dilaurate.
Preferably, the solvent is at least one of ethyl acetate and propylene glycol methyl ether.
More preferably, the solvent is a mixed solvent of ethyl acetate and propylene glycol methyl ether, and the mass ratio of the ethyl acetate to the propylene glycol methyl ether is 1.
Preferably, the solid content of the prepolymer is 85-90%, the viscosity is 3000-4500 cps, the appearance is clear and transparent, the molecular weight is 4000-5000, and the iodine value is 60-70 g/100g.
Preferably, the hydroxyl number of the hydroxyl-terminated hyperbranched polyester is 12, the molecular weight is 1200-1300, and the hydroxyl value is 480-520 mg KOH/g.
Preferably, the monomer raw materials are 24-26 parts of isocyanate, 2-3 parts of hydroxyl-terminated hyperbranched polyester, 24-26 parts of hydroxyl acrylate and 40-50 parts of fluorinated acrylate respectively according to molar parts.
More preferably, the catalyst is used in an amount of 0.2 to 0.5wt% based on the total mass of the monomers, and the solvent is used in an amount of 10 to 15wt% based on the total mass of the monomers. The monomers include isocyanate, hydroxyl-terminated hyperbranched polyester, hydroxyl acrylate and fluorinated acrylate.
The invention also relates to a preparation method of the photocuring polyurethane acrylate prepolymer, which comprises the following steps:
(1) Pretreatment: adding isocyanate and a catalyst into a solvent, and mixing to obtain an isocyanate solution;
(2) And (3) synthesis of hyperbranched polyurethane: adding hydroxyl-terminated hyperbranched polyester into an isocyanate solution to obtain hyperbranched polyurethane mixed solution;
(3) Prepolymer synthesis: adding hydroxyl acrylate into the hyperbranched polyurethane mixed solution, and then adding fluorinated acrylate to obtain the product.
Preferably, the step (2) is specifically: under the condition of inert gas, dripping the hydroxyl-terminated hyperbranched polyester into an isocyanate solution at the temperature of 45-60 ℃, and preserving the heat for 0.5-2 h to obtain hyperbranched polyurethane mixed solution.
More preferably, the inert gas comprises nitrogen.
Preferably, step (3) is specifically: heating the hyperbranched polyurethane mixed solution to 70-75 ℃, dropwise adding hydroxyl acrylate, cooling to 40-45 ℃, adding fluorinated acrylate, and keeping the temperature for 2.0-2.5 hours to obtain the hyperbranched polyurethane.
More preferably, the preparation method comprises the following steps:
(1) Pretreatment: adding isocyanate and a catalyst into a solvent, and mixing to obtain an isocyanate solution;
(2) And (3) synthesis of hyperbranched polyurethane: under the condition of inert gas, dripping hydroxyl-terminated hyperbranched polyester into an isocyanate solution at the temperature of 45-60 ℃, and preserving heat for 0.5-2 h to obtain hyperbranched polyurethane mixed solution;
(3) Prepolymer synthesis: heating the hyperbranched polyurethane mixed solution to 70-75 ℃, dropwise adding hydroxyl acrylate, cooling to 40-45 ℃, adding fluorinated acrylate, and keeping the temperature for 2.0-2.5 hours to obtain the hyperbranched polyurethane.
The invention also relates to a hardened coating liquid, and the raw materials comprise the photo-curing polyurethane acrylate prepolymer or the photo-curing polyurethane acrylate prepolymer prepared by the preparation method.
Preferably, the hardening coating liquid comprises, by weight, 50-55 parts of a photo-curing urethane acrylate prepolymer, 1-1.5 parts of a high-functionality active monomer, 3-4 parts of a photoinitiator, 0.5-1 part of wear-resistant nanoparticles and 30-45 parts of a solvent.
More preferably, the high functionality reactive monomer comprises a high functionality acrylate having a functionality of 10 to 15.
More preferably, the wear resistant nanoparticles comprise at least one of nano silicon carbide, nano zirconium dioxide, nano aluminum oxide and nano boron nitride.
The photoinitiator is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers. The photoinitiator is not specifically limited, and examples include German BASF IRGACURE127, 2959 photoinitiator, 184 photoinitiator, 1173 photoinitiator, 907 photoinitiator, TPO-L photoinitiator, IHT-PI 910 photoinitiator, 659 photoinitiator, MBF photoinitiator, IHT-PI 4265 photoinitiator, IHT-PI 1000 photoinitiator, and IHT-PI 500 photoinitiator.
The solvent is not particularly limited in the present invention, and propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-propanol, n-butyl acetate, methyl ethyl ketone and methyl isobutyl ketone may be mentioned.
The invention has the beneficial effects that:
the invention provides a photo-curing urethane acrylate prepolymer, which can control unsaturated functional groups of the prepolymer and balance the hardness of a coating by optimizing the hydroxyl number, the hydroxyl value and the molecular weight of hydroxyl-terminated hyperbranched polyester in synthetic raw materials of the photo-curing urethane acrylate prepolymer; and the terminal active group of the hydroxyl-terminated hyperbranched polyester is utilized to graft fluorinated acrylate through isocyanate as a middle bridge, so as to synthesize the prepolymer with high wear resistance and certain flexibility.
The invention takes isocyanate as a bridging, connects the hydroxyl acrylate at the tail end of the hydroxyl-terminated hyperbranched polyester, leads the hyperbranched polyester to have polymerization reaction at the tail end to generate polyurethane acrylate prepolymer, can improve the defect of poor toughness of the hyperbranched polyester, and the inventor finds that the invention is beneficial to controlling the molecular weight and crosslinking degree of the prepolymer by controlling the content of double bonds in the hydroxyl acrylate, thereby promoting the balance of toughness and hardness.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and substitutions are intended to be within the scope of the invention.
Photo-curing polyurethane acrylate prepolymer
In one embodiment, the method for preparing the prepolymer of the present invention comprises the steps of:
(1) Pretreatment: adding isocyanate and a catalyst into a solvent, and mixing to obtain an isocyanate solution;
(2) And (3) synthesis of hyperbranched polyurethane: the reaction flask was charged with nitrogen to displace the air in the flask. Dripping the hydroxyl-terminated hyperbranched polyester into an isocyanate solution at 50 ℃, and preserving heat for 1h to obtain a hyperbranched polyurethane mixed solution;
(3) Prepolymer synthesis: and heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding hydroxyl acrylate, cooling to 45 ℃, adding fluorinated acrylate, and keeping the temperature for 2.5 hours to obtain the photocuring polyurethane acrylate prepolymer.
The hyperbranched polymer has a three-dimensional structure and a large number of active end groups, a plurality of branched structures with approximate relative molecular mass and narrow relative molecular mass distribution extend from the core to the periphery, the compactness of the structures endow the hyperbranched polymer with special physical properties and chemical properties, the hyperbranched polymer is a highly branched dendrimer, and the hyperbranched polymer has the advantages of less intermolecular winding, low viscosity, easiness in film formation, high reaction activity, good solubility and the like. The hyperbranched polymer contains a large number of terminal groups which can be modified, and a large number of active terminal groups have great influence on the properties of the hyperbranched polymer, such as viscosity, solubility, thermal stability, glass transition temperature, relative molecular mass distribution and the like. Hyperbranched polyester is widely applied to thermosetting resin, medicines, coatings and the like, but has poor flexibility and larger brittleness. Different hyperbranched polyesters have different hydroxyl numbers, hydroxyl values and molecular weights, and have different properties. According to the invention, by selecting proper hydroxyl number, hydroxyl value and molecular weight, the unsaturated functional group of the prepolymer can be controlled, and the hardness of the coating and the crosslinking density of the coating are balanced; and the terminal active group of the hydroxyl-terminated hyperbranched polyester is utilized to graft fluorinated acrylate through isocyanate as a middle bridge, so as to synthesize the prepolymer with high wear resistance and certain flexibility.
Preferably, the hydroxyl number of the hydroxyl-terminated hyperbranched polyester selected by the invention is 4-24, the molecular weight is 600-4000, and the hydroxyl value is 300-520 mg KOH/g.
More preferably, the hydroxyl-terminated hyperbranched polyester selected by the invention has the hydroxyl number of 12, the molecular weight of 1200-1300, the hydroxyl value of 480-520 mg KOH/g and the proportion of 2-3 mol percent based on the total monomers. More preferably, the hydroxyl-terminated hyperbranched polyester of the invention is hebott Hyper H102.
Examples of aliphatic diisocyanates include, but are not limited to, one or more of tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate. More preferably, the aliphatic diisocyanate of the present invention is more excellent in at least one of tetramethylene diisocyanate and tetramethylhexane diisocyanate.
In a preferred embodiment, the monofunctional monohydroxy acrylate of the present invention includes, but is not limited to, one or more of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 3-hydroxy-1-adamantyl methacrylate (CAS No.: 115372-36-6), caprolactone acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate. More preferably, 2-hydroxy-3-phenoxypropyl acrylate is selected for use in the present invention.
The inventor finds that the defect of poor toughness of the hyperbranched polyester can be improved by connecting the hydroxyl acrylate to the tail end of the hydroxyl-terminated hyperbranched polyester through isocyanate serving as a bridging link to ensure that the polymerization reaction is carried out on the tail end of the hyperbranched polyester to generate the polyurethane acrylate prepolymer, and the inventor finds that the balance of the toughness and the hardness can be promoted by controlling the content of double bonds in the hydroxyl acrylate to be beneficial to controlling the molecular weight and the crosslinking degree of the prepolymer.
More preferably, the fluorinated acrylate is present in an amount of 40 to 50 mole percent based on the total monomers.
More preferably, the fluorinated acrylate is 4 fluoropropyl methacrylate. Fluorine in the fluorinated acrylate has high electronegativity and strong electron cloud binding capacity for electron bonding, and is favorable for forming hydrogen bonds with amino and hydroxyl of PUA, so that the polymerization efficiency of the fluorinated acrylate is increased, and the molecular weight and viscosity of the finally formed prepolymer are controlled to be proper by controlling the temperature, so that the balance of toughness and hardness is ensured, the hydrogen bonds form physical cross-linking points, the improvement of hardness and toughness is facilitated, and the existence of fluorine atoms is favorable for increasing a contact angle and reducing surface energy, so that the wear resistance is increased. In addition, due to the larger steric hindrance of fluorine atoms, the polymerization rate of the fluorinated acrylate is slower, and the fluorinated acrylate and the hydroxyl acrylate are favorably copolymerized to form a structure containing a fluorine substituent and a hydroxyl substituent alternately, so that hydrogen bonds are more easily formed, and the toughness and the hardness are favorably improved.
The prepolymer has the solid content of 85-90 percent, the viscosity of 3000-4500 cps, clear and transparent appearance, the molecular weight of 4000-5000 and the iodine value of 60-70 g/100g.
The hardening coating liquid comprises, by weight, 50-55 parts of a polyurethane acrylate prepolymer, 1-1.5 parts of a high-functionality active monomer, 3-4 parts of a photoinitiator, 0.5-1 part of wear-resistant nanoparticles and 30-45 parts of a solvent.
The high functionality active monomer is selected from the high functionality active monomer of the Fengjin 5894.
The photoinitiator is selected from German BASF IRGACURE127 and TPO.
German basf IRGACURE127 is a novel high-efficiency non-yellowing ultraviolet initiator, and is used for initiating the UV polymerization reaction of an unsaturated prepolymerization system. It has the following characteristics: 1. compared with the traditional alpha-hydroxy ketone photoinitiator, the photoinitiator has better reactivity. 2. Low sensitivity to oxygen inhibition. 3. Low volatility and low odor after curing.
TPO-diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus has wide absorption spectrum range and typical characteristics of low yellowing, and the TPO is more suitable for varnish and is especially suitable for a system with low odor requirement.
The wear-resistant nano particles are NANOBYK-3610, the nano particles are aluminum oxide, the particle size is 20nm, and the content is 30%.
The solvent is propylene glycol methyl ether.
The HyPer H10 series test indexes are shown in Table 1.
TABLE 1
| HyPer | H101 | H102 | H103 | H104 |
| Number of hydroxyl groups | 6 | 12 | 24 | 48 |
| Hydroxyl number (mg KOH/g) | 553 | 519 | 499 | 494 |
| Molecular weight | 600 | 1250 | 2650 | 5450 |
Basic example 1
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 2.
TABLE 2
The preparation method of the prepolymer comprises the following steps:
pretreatment: adding tetramethylene diisocyanate and dibutyltin dilaurate into a solvent (a mixed solvent of ethyl acetate and propylene glycol monomethyl ether, the mass ratio of the ethyl acetate to the propylene glycol monomethyl ether is 1), and mixing to obtain a tetramethylene diisocyanate solution, wherein the using amount of dibutyltin dilaurate is 0.3% of the total mass of the monomers, and the total mass of the solvent is 15% of the total mass of the monomers;
and (3) synthesis of hyperbranched polyurethane: the reaction flask was filled with nitrogen gas to displace the air in the reaction flask. Dripping H102 hyperbranched polyester into a tetramethylene diisocyanate solution at 50 ℃, and preserving heat for 1H to obtain a hyperbranched polyurethane mixed solution;
prepolymer synthesis: and (3) heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding 2-hydroxy-3-phenoxypropyl acrylate, cooling to 45 ℃, adding 4-fluoropropyl methacrylate, and preserving heat for 2.5 hours to obtain a prepolymer.
Basic example 2
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 3.
TABLE 3
The preparation method of the prepolymer comprises the following steps:
pretreatment: adding tetramethylenehexane diisocyanate and dibutyltin dilaurate into a solvent (a mixed solvent of ethyl acetate and propylene glycol methyl ether, the mass ratio of the ethyl acetate to the propylene glycol methyl ether is 1) and mixing to obtain a tetramethylenehexane diisocyanate solution, wherein the using amount of dibutyltin dilaurate is 0.3% of the total mass of the monomers, and the total mass of the solvent is 15% of the total mass of the monomers;
and (3) synthesis of hyperbranched polyurethane: the reaction flask was filled with nitrogen gas to displace the air in the reaction flask. Dripping H102 hyperbranched polyester into a tetramethylene diisocyanate solution at 50 ℃, and preserving heat for 1H to obtain a hyperbranched polyurethane mixed solution;
prepolymer synthesis: and (3) heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding 2-hydroxy-3-phenoxypropyl acrylate, cooling to 45 ℃, adding 4-fluoropropyl methacrylate, and preserving heat for 2.5 hours to obtain a prepolymer.
Basic example 3
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 4.
TABLE 4
The preparation method of the prepolymer comprises the following steps:
pretreatment: adding tetramethylene diisocyanate and dibutyltin dilaurate into a solvent (a mixed solvent of ethyl acetate and propylene glycol monomethyl ether, the mass ratio of the ethyl acetate to the propylene glycol monomethyl ether is 1), and mixing to obtain a tetramethylene diisocyanate solution, wherein the using amount of dibutyltin dilaurate is 0.3% of the total mass of the monomers, and the total mass of the solvent is 15% of the total mass of the monomers;
and (3) synthesis of hyperbranched polyurethane: the reaction flask was filled with nitrogen gas to displace the air in the reaction flask. Dripping H102 hyperbranched polyester into a tetramethylene diisocyanate solution at 50 ℃, and preserving heat for 1H to obtain a hyperbranched polyurethane mixed solution;
prepolymer synthesis: and (3) heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding 2-hydroxy-3-phenoxypropyl acrylate, cooling to 45 ℃, adding 4-fluoropropyl methacrylate, and preserving heat for 2 hours to obtain a prepolymer.
Basic example 4
The molar ratio of the monomers used to synthesize the prepolymer was determined, and the formulation is shown in Table 5.
TABLE 5
The preparation method of the prepolymer comprises the following steps:
pretreatment: adding tetramethylene diisocyanate and dibutyltin dilaurate into a solvent (a mixed solvent of ethyl acetate and propylene glycol monomethyl ether, the mass ratio of the ethyl acetate to the propylene glycol monomethyl ether is 1), and mixing to obtain a tetramethylene diisocyanate solution, wherein the using amount of dibutyltin dilaurate is 0.3% of the total mass of the monomers, and the total mass of the solvent is 15% of the total mass of the monomers;
and (3) synthesis of hyperbranched polyurethane: the reaction flask was charged with nitrogen to displace the air in the flask. Dripping H102 hyperbranched polyester into a tetramethylene diisocyanate solution at 50 ℃, and preserving heat for 1H to obtain a hyperbranched polyurethane mixed solution;
prepolymer synthesis: and (3) heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding 2-hydroxy-3-phenoxypropyl acrylate, cooling to 45 ℃, adding 4-fluoropropyl methacrylate, and preserving heat for 2.5 hours to obtain a prepolymer.
Basic comparative example 1
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 6.
TABLE 6
The preparation method of the prepolymer was the same as in example 1.
Basic comparative example 2
The molar ratio of the monomers used to synthesize the prepolymer was determined, and the formulation is shown in Table 7.
TABLE 7
The preparation of the prepolymer was carried out in the same manner as in example 1.
Basic comparative example 3
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 8.
TABLE 8
The preparation of the prepolymer was carried out in the same manner as in example 1.
Basic comparative example 4
The molar ratio of the monomers used to synthesize the prepolymer was calculated and the formula is shown in Table 9.
TABLE 9
The preparation method of the prepolymer was the same as in example 1.
Basic comparative example 5
The molar ratio of the monomers used to synthesize the prepolymer was determined, and the formulation is shown in Table 10.
Watch 10
The preparation method of the prepolymer was the same as in example 1.
Basic comparative example 6
The monomer formula for synthesizing the prepolymer is the same as that in example 1, the difference is only that the synthesis steps of the prepolymer are different, and the method specifically comprises the following steps:
pretreatment: adding tetramethylene diisocyanate and dibutyltin dilaurate into a solvent (a mixed solvent of ethyl acetate and propylene glycol monomethyl ether, the mass ratio of the ethyl acetate to the propylene glycol monomethyl ether is 1) and mixing to obtain a tetramethylene diisocyanate solution, wherein the using amount of the dibutyltin dilaurate is 0.3% of the total mass of the monomers, and the total mass of the solvent is 15% of the total mass of the monomers;
and (3) synthesis of hyperbranched polyurethane: the reaction flask was filled with nitrogen gas to displace the air in the reaction flask. Dripping H102 hyperbranched polyester into a 50 ℃ tetramethylene diisocyanate solution, and preserving heat for 1H to obtain a hyperbranched polyurethane mixed solution;
prepolymer synthesis: and (3) heating the hyperbranched polyurethane mixed solution to 75 ℃, dropwise adding 2-hydroxy-3-phenoxypropyl acrylate, cooling to 45 ℃, adding 4 fluoropropyl methacrylate, and preserving heat for 4 hours to obtain a prepolymer.
Test example
1. The appearance and viscosity of the prepared prepolymer are detected
The detection method comprises the following steps: appearance: observing the color and the transparency of the prepolymer by naked eyes; viscosity: measured using a U.S. bleer fly dvnxbcp laminar viscometer.
The solid content determination method comprises the following steps: oven method
1. The principle is as follows: drying a sample with a certain mass for a certain time at a certain temperature under normal pressure, and expressing the solid content by the percentage of the mass of the heated sample to the mass of the sample before heating.
2. Determination of step size
(1) Three weighing bottles are taken, dried in an oven at 105 +/-2 ℃ for 1.5h, cooled in a drier for 30min and weighed as m1.
(2) Weigh 1-2 g (to the nearest 0.0001 g) of sample into a dried weighing flask and record as m.
(3) And (3) slightly rotating the weighing bottle to enable the sample to be uniformly distributed at the bottom of the weighing bottle, slightly opening the cover of the weighing bottle, placing the weighing bottle in an oven at the temperature of (105 +/-2), opening an air blower, drying for 3 hours, then tightly covering the bottle cover, placing the bottle cover in a dryer, cooling for 30min, and weighing to obtain a mark m2.
3. Calculation of results
The solid content of the sample is represented by mass fraction X, and the value is expressed by (%), and is calculated according to formula (1):
X＝(m2-m1)/(m-m1)×100％ (1)
in the formula:
m is the number of the weighed bottle and the sample before drying. Units are grams (g);
m 1-number of the weighed bottle mass. Units are grams (g);
m 2-the number of the weighed bottles and samples after drying. The unit is grams (g).
And (3) taking the arithmetic average value of the secondary parallel measurement, and obtaining the measurement result after the arithmetic average value is reduced to 0.1% according to GB/T8170-2008, wherein the difference of the two parallel measurement results is not more than 0.3%.
The specific assay results are shown in Table 11 below.
TABLE 11
| Appearance of the product | Viscosity cps | Solid content% | |
| Basic example 1 | Transparent and non-yellowing | 3800 | 84.9 |
| Basic example 2 | Transparent and non-yellowing | 3890 | 84.8 |
| Basic example 3 | Transparent and non-yellowing | 3789 | 84.8 |
| Basic example 4 | Transparent and non-yellowing | 3831 | 85.2 |
| Basic comparative example 1 | Transparent and non-yellowing | 3812 | 85.1 |
| Basic comparative example 2 | Transparent and non-yellowing | 3815 | 84.8 |
| Basic comparative example 3 | Transparent and non-yellowing | 3789 | 85.2 |
| Basic comparative example 4 | Transparent and non-yellowing | 3780 | 85.1 |
| Basic comparative example 5 | Transparent and non-yellowing | 3879 | 84.7 |
| Basic comparative example 6 | Transparent and non-yellowing | 5600 | 85.5 |
2. The weight average molecular weight of the prepared prepolymer is detected
Molecular weight: the results of the tests using a waters e2695 liquid chromatograph are shown in table 12.
TABLE 12
| Molecular weight | |
| Basic example 1 | 4600 |
| Basic example 2 | 4679 |
| Basic example 3 | 4578 |
| Basic example 4 | 4678 |
| Basic comparative example 1 | 4567 |
| Basic comparative example 2 | 4578 |
| Basic comparative example 3 | 4598 |
| Basic comparative example 4 | 4578 |
| Basic comparative example 5 | 4678 |
| Basic comparative example 6 | 5789 |
3. The iodine value of the prepared prepolymer is measured
Iodine value test method: dissolving a certain amount of sample in a solvent, firstly adding a Vickers (Wijs) reagent to react for a certain time, then adding a potassium iodide solution to react with the rest iodine chloride solution, titrating the separated iodine by using a sodium thiosulfate solution, adding a starch solution indicator when the titration end point is approached, and continuing to titrate until blue color just disappears, namely the titration end point. The main chemical reaction formula is as follows:
R 1 CH＝CR 2 +ICl→R 1 CHI—CHClR 2 .................. (1)
ICl+KI→KCl+I 2 ..........................................(2)
I 2 +2NaS 2 O 3 →2Na I+Na 2 S 4 O 6 ...........................(3)
iodine value calculation formula W1= (V) 0 -V)*C*12.690/m
Wherein W1- -iodine value is expressed in grams of iodine taken up per 100g of sample (g/100 g);
m-sample mass, g;
c- -concentration of sodium thiosulfate standard solution, mol/L;
v- -the volume of the sodium thiosulfate standard solution consumed in titrating the sample, mL;
V 0 volume of sodium thiosulfate standard solution consumed for titration of the blank, mL.
The results are shown in Table 13.
Watch 13
| Iodine g/100g | |
| Basic example 1 | 62 |
| Basic example 2 | 64 |
| Basic example 3 | 66 |
| Basic example 4 | 61 |
| Basic comparative example 1 | 65 |
| Basic comparative example 2 | 67 |
| Basic comparative example 3 | 64 |
| Basic comparative example 4 | 65 |
| Basic comparative example 5 | 64 |
| Basic comparative example 6 | 45 |
Application example 1
The optical hardening coating liquid has the raw material weight percentage formula shown in table 14.
TABLE 14
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Application example 2
The optical hardening coating liquid has the raw material weight percentage formula shown in table 15.
Watch 15
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Application example 3
The optical hardening coating liquid has the raw material weight percentage formula shown in the table 16.
TABLE 16
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Application example 4
The optical hardening coating liquid has the raw material weight percentage formula shown in table 17.
TABLE 17
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Application comparative example 1
The optical hardening coating liquid has the raw material weight percentage formula shown in table 18.
Watch 18
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Comparative application example 2
The optical hardening coating liquid has the raw material weight percentage formula shown in table 19.
Watch 19
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Comparative application example 3
The optical hardening coating liquid has the raw material weight percentage formula shown in table 20.
Watch 20
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Comparative application example 4
The optical hardening coating liquid has the raw material weight percentage formula shown in table 21.
TABLE 21
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Comparative application example 5
The optical hardening coating liquid has the raw material weight percentage formula shown in table 22.
TABLE 22
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Comparative application example 6
The optical hardening coating liquid has the raw material weight percentage formula shown in table 23.
TABLE 23
The preparation method comprises the following steps: and mixing the prepared raw materials to obtain the optical hardening coating liquid.
Test example:
the optical hardening coating liquids prepared in application examples 1 to 4 and application comparative examples 1 to 6 were coated on a 50 μm cPI base film with the coating surface being an air surface, and then baked in an oven atmosphere of 60 degrees for 5 minutes, and the solvent was dried. UV curing is carried out under the protection of nitrogen, and the UV energy is 2000mj/cm 2 Preparing a transparent hardened CPI optical film; the thickness of the hardened layer in the optical film is 10 μm.
Each set was coated with 5 samples, and the following experiment was performed as an experimental sample.
Initial water drop angle test
The test is carried out by adopting a water drop angle tester of model JC2000D1 in the morning. The results are shown in Table 24.
TABLE 24
| Water drop angle/° | |
| Application example 1 | 106.7 |
| Application example 2 | 106.6 |
| Application example 3 | 106.4 |
| Application example 4 | 106.7 |
| Comparative application example 1 | 106.3 |
| Comparative application example 2 | 105.6 |
| Comparative application example 3 | 106.3 |
| Application comparative example 4 | 106.7 |
| Comparative application example 5 | 106.4 |
| Comparative application example 6 | 106.4 |
The water drop angles of the application examples 1-4 and the application comparative examples 1-6 are both more than or equal to 105 degrees, which shows that the fluorine carbon bond reduces the surface energy of the coating.
Second, dynamic bending test
The experimental method comprises the following steps: the test sample was tested by a Yuasa bending tester, and bent to the hardened coating side, the bending radius was R =1.5mm, and bending was performed at 180 ° for 20 ten thousand times to observe whether there was a crack, whitening, or the like. If not, it is labeled "pass" and if so, it is labeled "NG". The results are shown in Table 25.
TABLE 25
The coating is free from cracks in 20 ten thousand bending tests in application examples 1-4, cracks appear in 20 ten thousand dynamic bending tests in application comparative examples 1, 3, 4, 5 and 6, and no cracks appear in application comparative example 2, which shows that the application comparative example 2 is superior to other comparative examples in dynamic bending performance.
Hardness test
The hardened coating surface was tested for pencil hardness according to the absolute GB/T6739-2006 test standard, and the results are shown in Table 26.
Watch 26
| Hardness of | |
| Application example 1 | 5H |
| Application example 2 | 5H |
| Application example 3 | 5H |
| Application example 4 | 5H |
| Application comparative example 1 | 5H |
| Comparative application example 2 | 4H |
| Comparative application example 3 | 5H |
| Application comparative example 4 | 4H |
| Comparative application example 5 | 4H |
| Comparative application example 6 | 3H |
The pencil hardness of the coatings of application examples 1 to 4 and the coatings of application comparative examples 1 and 3 can reach 5H, and the pencil hardness of the coatings of application comparative examples 2,4, 5 and 6 can only reach 4H or lower.
And fourthly, an elongation at break test experiment method:
the coatings were tested for elongation at break according to the method specified in GB/T30776-2014, and the results are shown in Table 27.
Watch 27
The elongation at break of the coatings of application examples 1-4 is more than 4%, the elongation at break of the coatings of application comparative examples is less than 4%, and the toughness of the coatings is obviously poor.
Fifth, steel wool test
The test method comprises the following steps:
and (4) testing standard: the load of a grinding head is 1000g at 2cm x 2cm, the steel wool is 0000#, and the test speed is 40 times/min.
And (3) placing the base film on a test platform, and repeatedly rubbing the steel wool under the conditions until the surface of the hardened coating is scratched. The results are shown in Table 28: "pass" means no scratch after 2000 rubs and "NG" means scratch after 2000 rubs.
Watch 28
| 2000 times steel wool | |
| Application example 1 | pass |
| Application example 2 | pass |
| Application example 3 | pass |
| Application example 4 | pass |
| Comparative application example 1 | NG |
| Comparative application example 2 | pass |
| Comparative application example 3 | NG |
| Application comparative example 4 | NG |
| Comparative application example 5 | NG |
| Comparative application example 6 | NG |
After 2000 times of steel wool friction, the surfaces of the coatings of the application examples 1 to 4 and the coating of the application comparative example 2 are not scratched; after 2000 times of steel wool, scratches with different depths appear on the surfaces of the coatings of comparative examples 1, 3, 4, 5 and 6.
Test of Eraser
And (4) testing standard: the load of the minoan eraser is 1000g, and the test speed is 40 times/min.
The base film was placed on a test platform, and the rubber was rubbed repeatedly under the above conditions, and the water drop angle of the rubber was measured after 1000 rubs, and the results are shown in table 29.
TABLE 29
According to the detection results, the urethane acrylate prepolymers prepared in the basic examples 1 to 4 are used for preparing the optical hardening liquid, so that the elongation at break and the bending property of the hardened coating can be improved, and the prepared hardened coating has better steel wool resistance and eraser resistance.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. The hardening coating liquid is characterized by comprising 50-55 parts by weight of photo-curing urethane acrylate prepolymer, 1-1.5 parts by weight of high-functionality active monomer, 3-4 parts by weight of photoinitiator, 0.5-1 part by weight of wear-resistant nanoparticles and 30-45 parts by weight of solvent;
the photo-curing urethane acrylate prepolymer comprises the following raw materials: isocyanate, hydroxyl-terminated hyperbranched polyester, hydroxyl acrylate, fluorinated acrylate, a catalyst and a solvent; the hydroxyl number of the hydroxyl-terminated hyperbranched polyester is 12, the molecular weight is 1200-1300, and the hydroxyl value is 480-520 mg KOH/g;
according to the molar parts, the use amounts of the monomer raw materials are respectively 24-26 parts of isocyanate, 2-3 parts of hydroxyl-terminated hyperbranched polyester, 24-26 parts of hydroxyl acrylate and 40-50 parts of fluorinated acrylate;
the hydroxyl acrylate is single-functionality monohydroxy acrylate;
the fluorinated acrylate has 4 to 5 fluorine substitution numbers and a functionality of 2.
2. The hardening coating liquid according to claim 1, wherein the isocyanate is an aliphatic diisocyanate.
3. The hardening coating liquid according to claim 1, wherein the catalyst is dibutyltin dilaurate.
4. The hardening coating liquid according to claim 1, wherein the solvent is at least one of ethyl acetate and propylene glycol methyl ether.
5. The hardening coating liquid according to claim 4, wherein the solvent is a mixed solvent of ethyl acetate and propylene glycol methyl ether, and the mass ratio of the two is 1.
6. The hardening coating liquid as claimed in claim 1, wherein the prepolymer has a solid content of 85-90%, a viscosity of 3000-4500 cps, a clear and transparent appearance, a molecular weight of 4000-5000, and an iodine value of 60-70 g/100g.
7. The hardening coating liquid according to claim 1, wherein the catalyst is used in an amount of 0.2 to 0.5wt% based on the total mass of the monomers, and the solvent is used in an amount of 10 to 15wt% based on the total mass of the monomers.
8. The hardening coating liquid according to any one of claims 1 to 7, wherein the preparation method of the photo-curing urethane acrylate prepolymer comprises the following steps:
(1) Pretreatment: adding isocyanate and a catalyst into a solvent, and mixing to obtain an isocyanate solution;
(2) And (3) synthesis of hyperbranched polyurethane: adding hydroxyl-terminated hyperbranched polyester into an isocyanate solution to obtain hyperbranched polyurethane mixed solution;
(3) Prepolymer synthesis: adding hydroxyl acrylate into the hyperbranched polyurethane mixed solution, and then adding fluorinated acrylate to obtain the product.
9. The hardening coating liquid according to claim 8, wherein the step (2) is specifically: under the condition of inert gas, dripping the hydroxyl-terminated hyperbranched polyester into an isocyanate solution at the temperature of 45-60 ℃, and preserving the heat for 0.5-2 h to obtain hyperbranched polyurethane mixed solution.
10. A hardening coating liquid according to claim 8, characterized in that step (3) is specifically: heating the hyperbranched polyurethane mixed solution to 70-75 ℃, dropwise adding hydroxyl acrylate, cooling to 40-45 ℃, adding fluorinated acrylate, and keeping the temperature for 2.0-2.5 hours to obtain the hyperbranched polyurethane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60255879A (en) * | 1984-05-30 | 1985-12-17 | Sunstar Giken Kk | Polyurethane adhesive |
| WO1996038490A1 (en) * | 1995-05-31 | 1996-12-05 | Basf Coatings Aktiengesellschaft | Coating agent based on a hydroxyl group-containing polyacrylate resin and its use in processes for producing a multicoat paint system |
| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
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| CN110527032B (en) * | 2019-09-12 | 2022-03-01 | 山东格润高分子材料有限公司 | Light-cured resin material and preparation method thereof |
| CN110734698A (en) * | 2019-11-27 | 2020-01-31 | 上海金門量子科技有限公司 | hardening coating liquid for flexible cover plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60255879A (en) * | 1984-05-30 | 1985-12-17 | Sunstar Giken Kk | Polyurethane adhesive |
| WO1996038490A1 (en) * | 1995-05-31 | 1996-12-05 | Basf Coatings Aktiengesellschaft | Coating agent based on a hydroxyl group-containing polyacrylate resin and its use in processes for producing a multicoat paint system |
| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
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