CN113604178B - Hot-melt optical adhesive with ultraviolet blocking function and preparation method thereof - Google Patents
Hot-melt optical adhesive with ultraviolet blocking function and preparation method thereof Download PDFInfo
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- CN113604178B CN113604178B CN202111030382.9A CN202111030382A CN113604178B CN 113604178 B CN113604178 B CN 113604178B CN 202111030382 A CN202111030382 A CN 202111030382A CN 113604178 B CN113604178 B CN 113604178B
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
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Abstract
The invention belongs to the technical field of optical adhesives, and particularly relates to a hot-melt optical adhesive with an ultraviolet blocking function and a preparation method thereof, wherein the hot-melt optical adhesive comprises the following components in parts by weight: 100 parts of a mixed copolymer; 1-5 parts of a coupling agent; 0.2-0.6 part of antioxidant; 0.1-0.6 part of light stabilizer; 5-10 parts of a water-blocking agent; the mixed copolymer is obtained by reacting 100:5-10:0.5-1:1-3:0.5-1 parts by weight of ethylene-vinyl acetate copolymer, a cross-linking agent, an ultraviolet-proof agent, an initiator and a polymerization initiator; the ultraviolet-proof agent consists of 4-methacrylamide salicylic acid and thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate, wherein the thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate is obtained by reacting citric acid with 2-aminoethanethiol to obtain an intermediate product and esterifying with methyl allyl alcohol.
Description
Technical Field
The invention belongs to the technical field of optical adhesives, and particularly relates to a hot-melt optical adhesive with an ultraviolet ray blocking function and a preparation method thereof.
Background
The outdoor display screen is installed outdoors and suffers from the greatest damage to the outdoor display screen by ultraviolet rays in wind, sunlight and particularly sunlight all the year round, in order to prolong the service life of the display screen, the display screen must be prevented from being damaged by ultraviolet ray irradiation, and most of optical glue used by the display screen at present does not have the function.
In the prior art, a few optical adhesives are added with ultraviolet absorbers to improve the ultraviolet shielding effect of the optical adhesives, the wavelength range of ultraviolet rays in sunlight is below 400nm, but most of the ultraviolet absorbers can only absorb ultraviolet rays with the wavelengths of 300-380nm, and the ultraviolet shielding effect of the optical adhesives needs to be enhanced. Meanwhile, the ultraviolet absorbent has the problems of poor compatibility and stability in the optical adhesive, and the ultraviolet shielding capability of the ultraviolet absorbent is reduced, so that the aging speed of the ultraviolet absorbent is accelerated.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a hot-melt optical adhesive with an ultraviolet ray blocking function and a preparation method thereof, and solves the problem that the ultraviolet ray blocking range of an optical adhesive used for a display is small and aging is accelerated.
(II) technical scheme
In order to solve the problems, the invention is realized by the following scheme:
a hot-melt optical adhesive with an ultraviolet blocking function comprises the following components in parts by weight: 100 parts of a mixed copolymer; 1-5 parts of a coupling agent; 0.2-0.6 part of antioxidant; 0.1-0.6 part of light stabilizer; 5-10 parts of a water-blocking agent;
the mixed copolymer is obtained by reacting 100:5-10:0.5-1:1-3:0.5-1 parts by weight of ethylene-vinyl acetate copolymer, a cross-linking agent, an ultraviolet-proof agent, an initiator and a polymerization initiator;
the ultraviolet-proof agent consists of 4-methacrylamide salicylic acid and thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate, wherein the thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate is obtained by reacting citric acid with 2-aminoethanethiol to obtain an intermediate product and then esterifying with methyl allyl alcohol.
Specifically, the ethylene-vinyl acetate copolymer has a VA content of 12-16% and a Melt Index (MI) of 15.
Specifically, the coupling agent is at least one of gamma propyl trimethoxy silane, N-gamma aminopropyl methyl dimethoxy and vinyl tri (methoxyethoxy) silane, and the water-blocking agent is at least one of ethylene-methacrylic acid copolymer, sodium polymethacrylate, polyacrylic acid, zinc methacrylate, zinc stearate, polyethylene, polypropylene and polyolefin elastomer.
Specifically, the crosslinking agent is at least one of divinylbenzene and high vinyl 1, 2-polybutadiene.
Specifically, the initiator is at least one of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, n-butyl 4, 4-di (tert-amylperoxy) valerate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxy-2-ethylhexanoate, and the polymerization initiator is azobisisobutyronitrile.
Specifically, the antioxidant comprises a primary antioxidant and a secondary antioxidant; the primary antioxidant is at least one of 2, 6-di-tert-butyl-p-methylphenol, styrenated phenol and 2, 6-di-tert-butyl-4-n-butylphenol; the auxiliary antioxidant is a phosphite antioxidant, and the primary antioxidant and the auxiliary antioxidant are mixed according to the mass ratio of 1: 1.
Specifically, the light stabilizer is at least one of 2- (2-hydroxy-3, 5-dibutyl tert-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-n-octoxybenzophenone, hexamethylphosphoric triamide, and 2-cyano-3, 3-diphenylacrylic acid-2-ethylhexyl ester.
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) mixing citric acid and 2-aminoethanethiol, adding the mixture into deionized water for dissolving, and then applying vacuum to remove water for reaction to obtain an intermediate product;
(2) Adding the intermediate product, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimidate and 4-dimethylaminopyridine into a dichloromethane solvent in an ice bath, stirring and mixing for 2 hours, dropwise adding methallyl alcohol, removing the solvent by using a rotary evaporator after the reaction is finished to obtain a concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate, weighing the product with equal mass, and uniformly mixing the product and 4-methacrylamidosalicylic acid to obtain the ultraviolet-proof agent;
(3) weighing ethylene-vinyl acetate copolymer, a cross-linking agent and an ultraviolet-proof agent according to a certain proportion, dissolving the ethylene-vinyl acetate copolymer, the cross-linking agent and the ultraviolet-proof agent in a toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen for bubbling for 20min, adding an initiator and a polymerization initiator, carrying out a polymerization reaction, evaporating the toluene solvent by using a rotary evaporator after the reaction is finished to obtain a concentrated solution, precipitating a product by using excessive ethyl ether, and drying to obtain a mixed copolymer;
(4) the mixed copolymer, the antioxidant, the coupling agent, the light stabilizer and the water-blocking agent are uniformly mixed according to a certain proportion, input into a casting machine, and subjected to plasticizing extrusion, stretching, traction and rolling to obtain the optical adhesive with the ultraviolet blocking function.
Specifically, the mass ratio of the citric acid to the 2-aminoethanethiol in the step (1) is 24-26:9-10, and the reaction is carried out under the conditions of heating to 145 ℃ for 5-6 h.
Specifically, the mass ratio of the intermediate product in the step (2), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, dichloromethane solvent and methallyl alcohol is 2-2.2:28-3:0.01-0.02:50-60:1-1.2, and the reaction is carried out under the condition of stirring at room temperature for 24 hours.
Specifically, the polymerization reaction condition in the step (3) is that the reactor is sealed and stirred for 8-12h at 90 ℃, and the drying condition is that the reactor is dried for 24h under vacuum at 30 ℃.
Compared with the prior art, the method of the invention has the following beneficial effects:
(1) the invention provides a hot melt optical cement with ultraviolet blocking function and a preparation method thereof, firstly, 4-methacrylamide salicylic acid and thiazolyl-2 (1H) -pyridone-4-formic acid allyl methyl ester form an ultraviolet absorbent, the ultraviolet absorbent and the cross-linking agent are connected by the addition polymerization reaction of alkenyl through the initiation of the initiator and the polymerization initiator, and the cross-linking agent is used as a bridge, abstracting a hydrogen atom from the ethylene-vinyl acetate copolymer under the action of an initiator to form a reactive free radical site, combining two polymer free radicals to form a polymer network, therefore, the uvioresistant absorbent is stably fused into the ethylene-vinyl acetate copolymer, the problem of poor compatibility and stability of the ethylene-vinyl acetate copolymer is solved, and the crosslinking density of the mixed copolymer is improved;
(2) The invention provides a hot-melt optical adhesive with an ultraviolet blocking function, which is organically compounded with an ultraviolet absorbent consisting of 4-methacrylamidosalicylic acid and thiazolyl-2 (1H) -pyridone-4-formic acid allyl ester, wherein the 4-methacrylamidosalicylic acid is used for shielding 280nm-320nm ultraviolet rays, and the thiazolyl-2 (1H) -pyridone-4-formic acid allyl ester is used for shielding 320nm-400nm ultraviolet rays, so that the shielding effect on 320nm-400nm ultraviolet rays in sunlight is realized, the damage of most ultraviolet rays to the optical adhesive is reduced, and the service life of the optical adhesive is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) mixing 2.4g of citric acid and 0.9g of 2-aminoethanethiol, adding the mixture into 100ml of deionized water for dissolving, then applying vacuum to remove water, heating to 140 ℃ and keeping for 6 hours for reaction to obtain an intermediate product;
(2) Adding 1g of intermediate product, 1.4g of 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride and 0.005g of 4-dimethylaminopyridine into 30g of dichloromethane solvent under ice bath, stirring and mixing for 2H, then dropwise adding 0.5g of methallyl alcohol, stirring for 24H at room temperature for reaction, removing the solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, weighing 1g of the product, and uniformly mixing with 1g of 4-methacrylamide salicylic acid to obtain the ultraviolet-proof agent;
(3) weighing 100gVA ethylene-vinyl acetate copolymer with the content of 12%, 5g divinylbenzene and 0.5g ultraviolet-proof agent according to the proportion, dissolving the ethylene-vinyl acetate copolymer, the 5g divinylbenzene and the 0.5g ultraviolet-proof agent in 250ml toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen, bubbling for 20min, adding 1g1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and 0.5g azobisisobutyronitrile, carrying out polymerization reaction, evaporating the toluene solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, precipitating a product by using excessive ethyl ether, and carrying out vacuum drying for 24h at 30 ℃ to obtain a mixed copolymer;
(4) 100g of mixed copolymer, 0.1g of 2, 6-di-tert-butyl-p-methylphenol, 0.1g of phosphite antioxidant, 1g of gamma propyl trimethoxy silane, 0.1g of 2- (2-hydroxy-3, 5-dibutyl tert-phenyl) -5-chlorobenzotriazole and 5g of ethylene-methacrylic acid copolymer are uniformly mixed, input into a casting machine, and subjected to plasticizing extrusion, stretching, traction and rolling to obtain the optical adhesive with the ultraviolet blocking function.
Example 2
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) mixing 5g of citric acid and 1.8g of 2-aminoethanethiol, adding the mixture into 200ml of deionized water for dissolving, then applying vacuum to remove water, and heating to 142 ℃ for 6 hours for reaction to obtain an intermediate product;
(2) adding 4.2g of intermediate product, 5.8g of 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride and 0.04g of 4-dimethylaminopyridine into 50g of dichloromethane solvent under ice bath, stirring and mixing for 2H, then dropwise adding 2.1g of methallyl alcohol, stirring for 24H at room temperature for reaction, removing the solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, weighing 3g of the product, and uniformly mixing with 3g of 4-methacrylamide salicylic acid to obtain the ultraviolet-proof agent;
(3) weighing 100gVA ethylene-vinyl acetate copolymer with the content of 14 percent, 8g divinyl benzene and 0.6g ultraviolet-proof agent according to the proportion, dissolving the mixture in 250ml toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen, bubbling for 20min, adding 1.5g1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and 0.7g azobisisobutyronitrile, carrying out polymerization reaction, evaporating the toluene solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, precipitating a product by using excessive ethyl ether, and carrying out vacuum drying for 24h at 30 ℃ to obtain a mixed copolymer;
(4) Uniformly mixing 100g of mixed copolymer, 0.2g of styrenated phenol, 0.2g of phosphite antioxidant, 1g of gamma-aminopropyl methyl dimethoxy, 0.1g of 2 hydroxyl-4-n-octoxy benzophenone and 6g of sodium polymethacrylate according to a proportion, inputting the mixture into a casting machine, and obtaining the optical adhesive with the ultraviolet ray blocking function through plasticizing, extruding, stretching, drawing and rolling. .
Example 3
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) mixing 2.6g of citric acid and 1g of 2-aminoethanethiol, adding the mixture into 100ml of deionized water for dissolving, then applying vacuum to remove water, and heating to 145 ℃ for 5 hours for reaction to obtain an intermediate product;
(2) adding 2.2g of intermediate product, 2.8g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.03g of 4-dimethylaminopyridine into 50g of dichloromethane solvent under ice bath, stirring and mixing for 2H, then dropwise adding 0.12g of methallyl alcohol, stirring for 24H at room temperature for reaction, removing the solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, weighing 1g of the product, and uniformly mixing with 1g of 4-methacrylamide salicylic acid to obtain the ultraviolet-proof agent;
(3) Weighing 50gVA wt% ethylene-vinyl acetate copolymer, 0.5g divinylbenzene, 0.1g ultraviolet-proof agent and dissolving in 100ml toluene solvent, heating the obtained mixture to 90 ℃ and continuously stirring, introducing nitrogen to bubble for 20min, adding 0.3g tert-butyl peroxy-2-ethyl hexanoate and 0.8g azobisisobutyronitrile, then carrying out polymerization reaction, evaporating the toluene solvent by a rotary evaporator after the reaction is finished to obtain concentrated solution, precipitating the product by excessive ethyl ether, and carrying out vacuum drying for 24h at 30 ℃ to obtain mixed copolymer;
(4) 50g of mixed copolymer, 0.3g of 2, 6-di-tert-butyl-4-n-butylphenol, 0.3g of phosphite antioxidant, 0.4g of vinyltri (methoxyethoxy) silane, 0.1g of 2-cyano-3, 3-diphenylacrylic acid-2-ethylhexyl ester and 5g of zinc stearate are uniformly mixed, input into a casting machine, and subjected to plasticizing extrusion, stretching, traction and rolling to obtain the optical adhesive with the ultraviolet ray blocking function.
Example 4
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) mixing 2.6g of citric acid and 1g of 2-aminoethanethiol, adding the mixture into 100ml of deionized water for dissolving, then applying vacuum to remove water, and heating to 140 ℃ for 5 hours for reaction to obtain an intermediate product;
(2) Adding 2.1g of intermediate product, 3g of 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride and 0.001g of 4-dimethylaminopyridine into 55g of dichloromethane solvent under ice bath, stirring and mixing for 2H, then dropwise adding 1.2g of methallyl alcohol, stirring for 24H at room temperature for reaction, removing the solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, weighing 1.5g of the product, and uniformly mixing with 1.5g of 4-methacrylamide salicylic acid to obtain the ultraviolet-proof agent;
(3) weighing 100gVA ethylene-vinyl acetate copolymer with the content of 16%, 10g high vinyl 1, 2-polybutadiene and 1g ultraviolet-proof agent according to the proportion, dissolving the mixture in 250ml toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen, bubbling for 20min, adding 2g4, 4-di (tert-amyl peroxy) n-butyl valerate and 1g azobisisobutyronitrile, carrying out polymerization reaction, evaporating the toluene solvent by a rotary evaporator after the reaction is finished to obtain concentrated solution, precipitating a product by using excessive ethyl ether, and carrying out vacuum drying for 24h at the temperature of 30 ℃ to obtain a mixed copolymer;
(4) uniformly mixing 100g of the mixed copolymer, 0.25g of 2, 6-di-tert-butyl-4-n-butylphenol, 0.3g of phosphite antioxidant, 1g of gamma propyl trimethoxy silane, 0.6g of hexamethyl phosphoric triamide and 10g of zinc methacrylate according to a proportion, inputting the mixture into a casting machine, and obtaining the optical cement with the ultraviolet ray blocking function through plasticizing extrusion, stretching, traction and rolling.
Comparative example 1
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) weighing 100gVA content 12% ethylene-vinyl acetate copolymer, 5g divinylbenzene, 0.5g 4-methacrylamidosalicylic acid, dissolving in 250ml toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen, bubbling for 20min, adding 1g1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and 0.5g azobisisobutyronitrile, carrying out polymerization reaction, evaporating the toluene solvent by using a rotary evaporator after the reaction is finished to obtain concentrated solution, precipitating the product by using excessive ethyl ether, and carrying out vacuum drying for 24h at 30 ℃ to obtain a mixed copolymer;
(2) 100g of mixed copolymer, 0.1g of 2, 6-di-tert-butyl-p-methylphenol, 0.1g of phosphite antioxidant, 1g of gamma propyl trimethoxy silane, 2g of 2- (2-hydroxy-3, 5-dibutyl tert-phenyl) -5-chlorobenzotriazole and 5g of ethylene-methacrylic acid copolymer are uniformly mixed, input into a casting machine, and subjected to plasticizing extrusion, stretching, traction and rolling to obtain the optical adhesive with the ultraviolet blocking function.
Comparative example 2
A preparation method of hot-melt optical adhesive with ultraviolet blocking function comprises the following steps:
(1) Mixing 2.4g of citric acid and 0.9g of 2-aminoethanethiol, adding the mixture into 100ml of deionized water for dissolving, then applying vacuum to remove water, heating to 140 ℃, keeping for 6 hours for reaction to obtain an intermediate product, weighing 1g of the intermediate product, and uniformly mixing the intermediate product and 1g of 4-methacrylamide salicylic acid to obtain an anti-ultraviolet agent;
(4) 100gVA weight percent of ethylene-vinyl acetate copolymer, 0.5g of ultraviolet inhibitor, 0.1g of 2, 6-di-tert-butyl-p-methylphenol, 0.1g of phosphite antioxidant, 1g of gamma propyl trimethoxy silane, 2g of 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethylcyclohexane, 0.6g of 2- (2-hydroxy-3, 5-dibutyl tertiary phenyl) -5-chlorobenzotriazole and 5g of ethylene-methacrylic acid copolymer are evenly mixed and then input into a casting machine, and the optical adhesive with ultraviolet barrier function is obtained through plasticizing extrusion, stretching, traction and rolling.
1) Mechanical property test:
the optical cement was tested for tensile strength and elongation at break using the cement tensile strength test method using an optical instrument, the optical cement prepared in examples 1-5 and comparative examples 1-2 was cut into 25mmx25mm test specimens, a universal tester was loaded at a rate of 2mm/min until the specimens were broken, and the tensile strength and elongation at break of the test specimens were recorded, and the test results are shown in table 1.
Table 1:
2) and (3) ultraviolet resistance test:
the optical glues obtained in examples 1 to 4 and comparative examples 1 to 2 were tested for their UV resistance using a UV transmission analyzer (UV-1000F, Lapsphere, USA) according to GB/T18830-2009. The evaluation indices of ultraviolet resistance include solar UV-A spectral transmittance T (UVA), solar UV-B spectral transmittance T (UVB), and Ultraviolet Protection Factor (UPF). Each sample was tested five times and averaged to provide the test results shown in table 2.
Table 2:
| item | T(UVB)％ | T(UVA)％ | UPF |
| Example 1 | 3.22 | 3.14 | 33.22 |
| Examples2 | 3.25 | 3.13 | 32.92 |
| Example 3 | 3.23 | 3.17 | 32.96 |
| Example 4 | 3.24 | 3.12 | 33.24 |
| Comparative example 1 | 4.32 | 8.23 | 22.52 |
| Comparative example 2 | 4.42 | 5.11 | 27.15 |
3) And (3) aging resistance testing:
the sample preparation method for the damp-heat resistant accelerated aging test comprises the following steps: the EVA optical adhesive film is clamped by two pieces of ultra-white glass with the thickness of 1mm from top to bottom, the specification of a sample is 100mm x 100mm, after prepressing and laminating by a vacuum laminating machine at the temperature of 80 ℃, the sample is prepared by irradiating for 90 seconds under a mercury lamp with the light intensity of 1200Mw and the main peak wavelength of 310-365nm to complete cross-linking and curing, the sample is divided into 4 groups, and the test is respectively carried out according to the following conditions: (1) the temperature is 60 ℃, the humidity is 90 percent, and the time is 240 h; (2) the temperature is 70 ℃, the humidity is 90 percent, and the time is 240 h; (3): the temperature is 80 ℃, the humidity is 90 percent, and the time is 240 h; (5): soaking in boiling water for 24 hr.
The performance characterization method comprises the following steps: A. observing whether the sample has abnormal changes such as bubbles, degumming, displacement, water inflow, yellowing and the like after the damp-heat accelerated aging; B. the light transmittance and the haze of the sample before and after the humid heat accelerated aging are detected and compared by referring to a method GB/T2410-2008 'determination of light transmittance and haze of transparent plastic', and the test result is shown in Table 3.
Table 3:
in summary, as can be seen from tables 1 and 3, the optical cement prepared in the examples of the present invention has better mechanical properties and aging resistance than the comparative examples, because the uv absorber and the cross-linking agent are linked by the addition polymerization of alkenyl groups, and the two polymer radicals are combined to form a polymer network, so that the uv absorber is stably fused into the ethylene-vinyl acetate copolymer, the cross-linking density of the hybrid copolymer is increased, and the problems of poor compatibility and stability are solved. As can be seen from Table 2, when UPF >30 and T (UVA), T (UVB)% < 5%, the samples can be called UV resistant products, the T (UVA) measured by the optical glue of the examples 1-4 is less than 3.2%, the T (UVB) is less than 3.3%, and the UPF is more than 32, which shows that the sample can reach the anti-ultraviolet level and can absorb most of the ultraviolet rays with the wavelength of 280-400nm, whereas the optical glues of comparative examples 1-2 had T (UVB) < 5%, but T (UVA) > 5%, and the UPF value is lower, which is mainly that in the embodiment of the invention, 4-methacrylamidosalicylic acid and thiazolyl-2 (1H) -pyridone-4-formic allyl ester form an ultraviolet absorbent and are organically combined with the ethylene-vinyl acetate copolymer of the optical gum base, so that the effect of synergistically enhancing the ultraviolet resistance of the protective film is achieved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A hot-melt optical adhesive with an ultraviolet blocking function is characterized by comprising the following components in parts by weight: 100 parts of a mixed copolymer; 1-5 parts of a coupling agent; 0.2-0.6 part of antioxidant; 0.1-0.6 part of light stabilizer; 5-10 parts of a water-blocking agent;
The mixed copolymer is obtained by reacting 100:5-10:0.5-1:1-3:0.5-1 parts by weight of ethylene-vinyl acetate copolymer, a cross-linking agent, an ultraviolet-proof agent, an initiator and a polymerization initiator;
the ultraviolet inhibitor consists of 4-methacrylamide salicylic acid and thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, and the thiazolyl-2 (1H) -pyridone-4-methyl allyl formate is obtained by reacting citric acid with 2-aminoethanethiol to obtain an intermediate product and then esterifying with methallyl alcohol;
the crosslinking agent is at least one of divinylbenzene and high vinyl 1, 2-polybutadiene, the initiator is at least one of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, 4-di (tert-amylperoxy) n-butyl valerate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxy-2-ethylhexanoate, and the polymerization initiator is azobisisobutyronitrile.
2. A hot-melt optical adhesive with ultraviolet ray blocking function according to claim 1, wherein the ethylene-vinyl acetate copolymer has a VA content of 12-16% and a Melt Index (MI) of 15.
3. A hot-melt optical adhesive with ultraviolet ray blocking function according to claim 1, wherein the coupling agent is at least one of gamma-propyltrimethoxysilane and vinyltris (methoxyethoxy) silane, and the water-blocking agent is at least one of ethylene-methacrylic acid copolymer, sodium polymethacrylate, polyacrylic acid, zinc methacrylate, zinc stearate, polyethylene, polypropylene and polyolefin elastomer.
4. A hot-melt optical adhesive having an ultraviolet blocking function according to claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant; the primary antioxidant is at least one of 2, 6-di-tert-butyl-p-methylphenol, styrenated phenol and 2, 6-di-tert-butyl-4-n-butylphenol; the auxiliary antioxidant is a phosphite antioxidant, and the primary antioxidant and the auxiliary antioxidant are mixed according to the mass ratio of 1: 1.
5. The hot-melt optical adhesive with ultraviolet ray blocking function according to claim 1, wherein the light stabilizer is at least one of 2- (2-hydroxy-3, 5-dibutyl tert-phenyl) -5-chlorobenzotriazole, 2-hydroxy-4-n-octyloxy benzophenone, hexamethylphosphoric triamide, and 2-cyano-3, 3-2-ethylhexyl diphenylacrylate.
6. The method for preparing the hot-melt optical adhesive with the ultraviolet ray blocking function according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) mixing citric acid and 2-aminoethanethiol, adding the mixture into deionized water for dissolving, and then applying vacuum to remove water for reaction to obtain an intermediate product;
(2) Adding the intermediate product, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimidate and 4-dimethylaminopyridine into a dichloromethane solvent in an ice bath, stirring and mixing for 2 hours, dropwise adding methallyl alcohol, removing the solvent by using a rotary evaporator after the reaction is finished to obtain a concentrated solution, drying to obtain a product, namely thiazolyl-2 (1H) -pyridinone-4-methyl allyl formate, weighing the product with equal mass, and uniformly mixing the product and 4-methacrylamidosalicylic acid to obtain the ultraviolet-proof agent;
(3) weighing ethylene-vinyl acetate copolymer, a cross-linking agent and an ultraviolet-proof agent according to a certain proportion, dissolving the ethylene-vinyl acetate copolymer, the cross-linking agent and the ultraviolet-proof agent in a toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen for bubbling for 20min, adding an initiator and a polymerization initiator, carrying out a polymerization reaction, evaporating the toluene solvent by using a rotary evaporator after the reaction is finished to obtain a concentrated solution, precipitating a product by using excessive ethyl ether, and drying to obtain a mixed copolymer;
(4) the mixed copolymer, the antioxidant, the coupling agent, the light stabilizer and the water-blocking agent are uniformly mixed according to a certain proportion, input into a casting machine, and subjected to plasticizing extrusion, stretching, traction and rolling to obtain the optical adhesive with the ultraviolet blocking function.
7. The method for preparing the hot-melt optical adhesive with the ultraviolet ray blocking function according to claim 6, wherein the mass ratio of the citric acid to the 2-aminoethanethiol in the step (1) is 24-26:9-10, and the reaction is carried out under the conditions of heating to 140 ℃ and 145 ℃ and keeping for 5-6 h.
8. The method for preparing the hot melt optical adhesive with the ultraviolet ray blocking function according to claim 6, wherein the mass ratio of the intermediate product in the step (2), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, methylene chloride solvent and methallyl alcohol is 2-2.2:28-3:0.01-0.02:50-60:1-1.2, and the reaction condition in the step (2) is that the reaction is carried out by stirring at room temperature for 24 hours.
9. A method for preparing the hot-melt optical adhesive with the ultraviolet ray blocking function according to claim 6, wherein the polymerization reaction condition in the step (3) is that the reactor is sealed and stirred at 90 ℃ for 8-12h, and the drying condition is that the reactor is dried in vacuum at 30 ℃ for 24 h.
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| KR20170121778A (en) * | 2016-04-25 | 2017-11-03 | 전면근 | Hot melt adhesion film |
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| CN111944455A (en) * | 2020-07-07 | 2020-11-17 | 深圳市高仁电子新材料有限公司 | High-weather-resistance blue-light-proof optical adhesive and film forming preparation method thereof |
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| KR20170121778A (en) * | 2016-04-25 | 2017-11-03 | 전면근 | Hot melt adhesion film |
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