CN113604178A - 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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- CN113604178A CN113604178A CN202111030382.9A CN202111030382A CN113604178A CN 113604178 A CN113604178 A CN 113604178A CN 202111030382 A CN202111030382 A CN 202111030382A CN 113604178 A CN113604178 A CN 113604178A
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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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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- 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 blocking function and a preparation method thereof.
Background
The outdoor display screen is installed outdoors and is subjected to wind and sun exposure, particularly ultraviolet rays in sunlight, most of the damage to the outdoor display screen is caused, in order to prolong the service life of the display screen, the display screen must be prevented from being damaged by ultraviolet irradiation, and most of optical adhesives used in the current displays do 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 wavelength 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 optical adhesive is reduced, so that the aging speed of the optical adhesive 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 optical adhesive used for a display has a small ultraviolet ray blocking range and is accelerated in aging.
(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) carbodiimide hydrochloride and 4-dimethylaminopyridine into a dichloromethane solvent under 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) -pyridone-4-methyl allyl formate, weighing the product with equal mass, and uniformly mixing the product and 4-methacrylamide salicylic acid to obtain an ultraviolet-proof agent;
(3) weighing ethylene-vinyl acetate copolymer, a cross-linking agent and an anti-ultraviolet agent according to a certain proportion, dissolving the ethylene-vinyl acetate copolymer, the cross-linking agent and the anti-ultraviolet 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 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, then the mixture is input into a casting machine, and the optical adhesive with the ultraviolet blocking function is obtained through plasticizing extrusion, stretching, traction and rolling.
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 condition of heating to 140-145 ℃ and keeping for 5-6 h.
Specifically, the mass ratio of the intermediate product in the step (2), the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 4-dimethylaminopyridine, the dichloromethane solvent and the 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 for 24 hours at room temperature.
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 vacuum drying for 24h at 30 ℃.
Compared with the prior art, the method has the beneficial effects that:
(1) the invention provides a hot melt optical adhesive with ultraviolet blocking function and a preparation method thereof, firstly, 4-methacrylamide salicylic acid and thiazolyl-2 (1H) -pyridone-4-methyl formate form an ultraviolet absorbent, the ultraviolet absorbent and the cross-linking agent are connected by the addition polymerization reaction of alkenyl through the initiation action 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-methyl allyl formate, wherein the ultraviolet with the wavelength of 280nm-320nm is shielded by the 4-methacrylamidosalicylic acid, and the ultraviolet with the wavelength of 320nm-400nm is shielded by the thiazolyl-2 (1H) -pyridone-4-methyl allyl formate, so that the shielding effect on the ultraviolet with the wavelength of 320nm-400nm 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 clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within 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) carbodiimide 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 an 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, heating to 142 ℃ and keeping the temperature for 6 hours for reaction to obtain an intermediate product;
(2) adding 4.2g of intermediate product, 5.8g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide 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 an 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 hydroxy-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 extrusion, stretching, traction 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, heating to 145 ℃ and keeping the temperature 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 an ultraviolet-proof agent;
(3) weighing and dissolving 50 gVA-content 13% ethylene-vinyl acetate copolymer, 0.5g of divinylbenzene and 0.1g of ultraviolet-proof agent in a 100ml toluene solvent according to a proportion, heating the obtained mixture to 90 ℃ and continuously stirring, introducing nitrogen for bubbling for 20min, adding 0.3g of tert-butyl peroxy-2-ethylhexanoate and 0.8g of azobisisobutyronitrile, carrying out 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 carrying out vacuum drying for 24h at 30 ℃ to obtain a 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 vinyl tri (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 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, heating to 140 ℃ and keeping the temperature for 5 hours for reaction to obtain an intermediate product;
(2) adding 2.1g of intermediate product, 3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide 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 an anti-ultraviolet 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 in 250ml toluene solvent, heating the obtained mixture to 90 ℃ while 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 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, 0.25g 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 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 ethylene-vinyl acetate copolymer with the content of 12%, 5g divinyl benzene and 0.5g 4-methacrylamidosalicylic acid, dissolving the mixture in 250ml toluene solvent, heating the obtained mixture to 90 ℃, continuously stirring, introducing nitrogen, bubbling for 20min, adding 1g1, 1-di-tert-butylperoxy-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;
(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 ℃ and keeping for 6 hours for reaction to obtain an intermediate product, weighing 1g of the intermediate product and 1g of 4-methacrylamide salicylic acid, and uniformly mixing to obtain the ultraviolet-proof agent;
(4) 100gVA ethylene-vinyl acetate copolymer with the content of 12 percent, 0.5g ultraviolet-proof agent, 0.1g2, 6-di-tert-butyl-p-methyl phenol, 0.1g phosphite antioxidant, 1g gamma propyl trimethoxy silane, 2g1, 1-di-tert-butyl peroxy-3, 3, 5-trimethyl cyclohexane, 0.6g2- (2-hydroxy-3, 5-dibutyl tertiary phenyl) -5-chloro benzotriazole and 5g ethylene-methacrylic acid copolymer are evenly 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.
1) Mechanical property test:
tensile strength and elongation at break of the optical cement were measured by means of a cement tensile strength test method using an optical instrument, the optical cement prepared in examples 1 to 5 and comparative examples 1 to 2 was cut into a sample of 25mmx25mm, a universal tester was loaded at a rate of 2mm/min until the sample was broken, and the tensile strength and elongation at break of the sample were recorded, and the results of the measurements are shown in table 1.
Table 1:
2) 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 index of ultraviolet resistance performance includes 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 obtain the test results shown in Table 2.
Table 2:
| item | T(UVB)％ | T(UVA)％ | UPF |
| Example 1 | 3.22 | 3.14 | 33.22 |
| Example 2 | 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 crosslinking agent are connected by the addition polymerization of the alkenyl group, 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 crosslinking 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) and T (UVB)% < 5%, the samples can be called UV resistant products, T (UVA) measured by the optical cement of the examples 1-4 is less than 3.2 percent, T (UVB) percent is less than 3.3 percent, UPF is greater than 32, which shows that the sample can reach the anti-ultraviolet level and can absorb most 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 acid methyl propylene ester form an ultraviolet absorbent and are organically combined with the optical gum base ethylene-vinyl acetate copolymer, 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 (10)
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-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.
2. The hot-melt optical adhesive with the ultraviolet blocking function according to claim 1, wherein the ethylene-vinyl acetate copolymer has a VA content of 12% to 16% and a Melt Index (MI) of 15.
3. The hot-melt optical adhesive with the ultraviolet ray blocking function as claimed in claim 1, wherein the coupling agent is at least one of gamma propyl trimethoxy silane, N-gamma aminopropyl methyl dimethoxy and vinyl tris (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. The optical adhesive of claim 1, wherein 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, 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.
5. 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.
6. The hot-melt optical adhesive with the ultraviolet 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-octoxybenzophenone, hexamethylphosphoric triamide and 2-cyano-3, 3-diphenylacrylic acid-2-ethylhexyl ester.
7. A method for preparing the hot-melt optical adhesive with the ultraviolet blocking function according to any one of claims 1 to 6, which 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) carbodiimide hydrochloride and 4-dimethylaminopyridine into a dichloromethane solvent under 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) -pyridone-4-methyl allyl formate, weighing the product with equal mass, and uniformly mixing the product and 4-methacrylamide salicylic acid to obtain an ultraviolet-proof agent;
(3) weighing ethylene-vinyl acetate copolymer, a cross-linking agent and an anti-ultraviolet agent according to a certain proportion, dissolving the ethylene-vinyl acetate copolymer, the cross-linking agent and the anti-ultraviolet 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 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, then the mixture is input into a casting machine, and the optical adhesive with the ultraviolet blocking function is obtained through plasticizing extrusion, stretching, traction and rolling.
8. The method as claimed in claim 7, wherein the mass ratio of citric acid to 2-aminoethanethiol in step (1) is 24-26:9-10, and the reaction is carried out under conditions of heating to 140-145 ℃ and maintaining for 5-6 h.
9. The method for preparing the hot melt optical adhesive with the ultraviolet ray blocking function according to claim 7, wherein 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 condition in the step (2) is that the reaction is carried out by stirring at room temperature for 24 hours.
10. The method for preparing the hot-melt optical adhesive with the ultraviolet blocking function according to claim 3, wherein 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 vacuum drying for 24h at 30 ℃.
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| KR20170121778A (en) * | 2016-04-25 | 2017-11-03 | 전면근 | Hot melt adhesion film |
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| KR20170121778A (en) * | 2016-04-25 | 2017-11-03 | 전면근 | Hot melt adhesion film |
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