CN111187590A - Weather-resistant and water-resistant photo-curing pressure-sensitive adhesive - Google Patents
Weather-resistant and water-resistant photo-curing pressure-sensitive adhesive Download PDFInfo
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- CN111187590A CN111187590A CN202010110241.7A CN202010110241A CN111187590A CN 111187590 A CN111187590 A CN 111187590A CN 202010110241 A CN202010110241 A CN 202010110241A CN 111187590 A CN111187590 A CN 111187590A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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Abstract
The invention discloses a weather-resistant and water-resistant photo-curing pressure-sensitive adhesive which is characterized by comprising the following components in parts by weight: 15-25 parts of valencene myrcene/pimaric acid/trifluoroethyl acrylate copolymer, 25-35 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 2-5 parts of polyethylene glycol diacrylate, 1-3 parts of photoinitiator, 5-10 parts of active diluent and 0.2-0.6 part of antioxidant. The invention also discloses a preparation method and application of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive. The weather-resistant and water-resistant photocuring pressure-sensitive adhesive disclosed by the invention is environment-friendly, and has the advantages of good weather resistance, aging resistance and water resistance, good high and low temperature resistance and high bonding strength.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a weather-resistant and water-resistant photo-curing pressure-sensitive adhesive and a preparation method thereof.
Background
In recent years, with the increasing awareness of environmental protection, the preparation technology of pressure-sensitive adhesives and products thereof has undergone the cross-over conversion from traditional solvent-based pressure-sensitive adhesives to emulsion-type and hot-melt pressure-sensitive adhesives. However, the water emulsion type has the defects of large energy consumption, reduced performance and the like, while the hot melt type process does not need a solvent, but has large energy consumption, and the pressure-sensitive adhesive has poor creep resistance and weather resistance. It is in this situation that photo-curable pressure-sensitive adhesives have come into force. The pressure-sensitive adhesive has high curing speed, no solvent, no pollution, environmental protection, safety, room temperature curing, low energy consumption and good water resistance and heat resistance, becomes the mainstream direction of the pressure-sensitive adhesive industry at the present stage and even for a period of time in the future, has larger market potential, and is a new star product in the market.
The photo-curing pressure-sensitive adhesive is a pressure-sensitive adhesive which is characterized in that a photosensitizer in a system forms active fragments under ultraviolet irradiation with proper wavelength and intensity, and then the active fragments initiate unsaturated monomers to polymerize, crosslink and the like so as to achieve the curing purpose.
In chinese patent publication No. CN103012728A, acrylate monomers are used as raw materials, a linear acrylate copolymer with a certain molecular weight and containing hydroxyl groups on side chains is generated by radical polymerization, a polymer containing a large amount of urethane groups is synthesized by polyurethane modification, and ultraviolet light curing is performed to prepare a pressure-sensitive adhesive, which has good wettability to metal, glass, ceramic, plastic and the like, and can be used for preparing a pressure-sensitive adhesive tape with good initial adhesion and excellent peel strength. However, the pressure-sensitive adhesive contains a solvent, and the pressure-sensitive adhesive is prepared by ultraviolet curing after the solvent is dried before use, and the problem of VOC emission still exists.
Therefore, the development of the photocuring pressure-sensitive adhesive which is environment-friendly, good in weather resistance, good in high and low temperature resistance and large in bonding strength meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the pressure-sensitive adhesive industry.
Disclosure of Invention
The invention aims to solve the problems and provides the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive and the preparation method thereof, the preparation method is simple and easy to implement, has low requirements on equipment and reaction conditions, low energy consumption, high preparation efficiency and yield, is suitable for continuous large-scale production, and has higher popularization and application values; the prepared photocuring pressure-sensitive adhesive is environment-friendly, and has good weather resistance, aging resistance and water resistance, good high and low temperature resistance and high bonding strength.
In order to achieve the purpose, the invention adopts the technical scheme that:
the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following components in parts by weight: 15-25 parts of valencene myrcene/pimaric acid/trifluoroethyl acrylate copolymer, 25-35 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 2-5 parts of polyethylene glycol diacrylate, 1-3 parts of photoinitiator, 5-10 parts of active diluent and 0.2-0.6 part of antioxidant.
Further, the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and 2-isopropyl thioxanthone.
Further, the reactive diluent is at least one of ethoxyethoxyethyl acrylate, isobornyl acrylate, lauric acid acrylate and tetrahydrofuran acrylate.
Further, the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further, the preparation method of the valencene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding the valencene/pimaric acid/trifluoroethyl acrylate copolymer into a high-boiling-point solvent, stirring and reacting for 3-5 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature, precipitating in water, washing the product with ethanol for 3-6 times, and then removing the ethanol by rotary evaporation to obtain the valencene/pimaric acid/trifluoroethyl acrylate copolymer.
Preferably, the mass ratio of the valencene to the pimaric acid to the trifluoroethyl acrylate to the initiator to the high-boiling-point solvent is 1:1:2 (0.03-0.05) to (14-20).
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the inert gas is one of helium, neon and argon.
Further, the preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving rosin-based hyperbranched epoxy resin and 3-aminocrotonitrile in an organic solvent, stirring and reacting for 4-6 hours at 30-50 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain vinyl modified rosin-based hyperbranched epoxy resin;
and S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 6-8 hours at the temperature of 30-40 ℃, and then performing rotary evaporation to remove the acetone to obtain the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin.
Preferably, the molar ratio of the rosin-based hyperbranched epoxy resin, the 3-aminocrotonitrile and the organic solvent in the step S1 is 1:6 (20-30).
Preferably, the organic solvent is any one of acetone, toluene and tetrahydrofuran.
Preferably, the molar ratio of the vinyl modified rosin-based hyperbranched epoxy resin, the 2-chloroethyltriethoxysilane and the acetone in the step S2 is 1:2 (10-16).
Preferably, the preparation method of the rosin-based hyperbranched epoxy resin refers to the following steps: chinese patent application No. 201610861045.7, example 1.
Preferably, the polyethylene glycol diacrylate is available from Shanghai light chemical industry Co., Ltd., Cat No.: 1027.
the invention also aims to provide a preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive, which comprises the following steps: mixing the components in parts by weight, performing ultrasonic dispersion for 10-20 minutes, and then stirring and reacting at 30-50 ℃ for 1-3 hours to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
Another aspect of the present inventionThe object is to provide the application of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive, wherein the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive is uniformly coated on a substrate by radiation dosage of 70-90mW cm-2Irradiating by ultraviolet light for 20-40 s to obtain the pressure-sensitive adhesive product.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive provided by the invention is simple and feasible, has low requirements on equipment and reaction conditions, is low in energy consumption, high in preparation efficiency and yield, suitable for continuous large-scale production, and has high popularization and application values.
(2) The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive provided by the invention overcomes the defects that the photo-curing pressure-sensitive adhesive in the prior art is poor in water resistance, cannot be used in a humid environment, is limited in temperature resistance and poor in bonding strength and weather resistance, and has the advantages of environmental friendliness, good weather resistance, ageing resistance and water resistance, good high and low temperature resistance and high bonding strength.
(3) The main components of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprise a valencene/pimaric acid/trifluoroethyl acrylate copolymer and vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, carboxyl on the valencene/pimaric acid/trifluoroethyl acrylate copolymer and quaternary ammonium salt cations on the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin are easily combined by ionic bonds, and a stable ionic cross-linking structure is formed during curing molding, so that the comprehensive performance of the pressure-sensitive adhesive is excellent, and double-end vinyl groups on a polyethylene glycol diacrylate molecular chain are cured under ultraviolet light to perform photo-initiated free radical polymerization reaction to form a three-dimensional network structure, thereby effectively improving the high and low temperature resistance and weather resistance of the pressure-sensitive adhesive.
(4) According to the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive, the added vinyl cyano-group ionized modified rosin-based hyperbranched epoxy resin is subjected to vinyl cyano-group ionized modification, vinyl is introduced, a reaction site can be formed for subsequent crosslinking and curing, cyano-group and quaternary ammonium salt cations are introduced, and an ethoxysilicon structure is also adopted, so that the bonding strength of the pressure-sensitive adhesive is effectively improved under the electronic effect and the bridging effect; the added valencene/pimaric acid/trifluoroethyl acrylate copolymer introduces each unit structure, which can effectively improve the adhesive property and the comprehensive property, so that the weather resistance, the water resistance and the aging resistance are better.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The preparation method of the rosin-based hyperbranched epoxy resin, which is related in the following embodiment of the invention, refers to: chinese invention patent example 1 with application number 201610861045.7; the polyethylene glycol diacrylate is purchased from Shanghai light chemical industry Co., Ltd, and has a product number of: 1027; other raw materials were all purchased commercially.
Example 1
The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises, by weight, 15 parts of valencene/pimaric acid/trifluoroethyl acrylate copolymer, 25 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 2 parts of polyethylene glycol diacrylate, 1 part of 1-hydroxycyclohexyl phenyl ketone, 5 parts of ethoxy ethyl acrylate, and 0.2 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the valencia mandarin ene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding baleneimine, pimaric acid, trifluoroethyl acrylate and azodiisobutyronitrile into dimethyl sulfoxide, stirring and reacting for 3 hours at 70 ℃ in the atmosphere of nitrogen, cooling to room temperature, precipitating in water, washing the product with ethanol for 3 times, and then performing rotary evaporation to remove the ethanol to obtain a baleneimine/pimaric acid/trifluoroethyl acrylate copolymer; the mass ratio of the valencene to the pimaric acid to the trifluoroethyl acrylate to the azodiisobutyronitrile to the dimethyl sulfoxide is 1:1:2:0.03: 14.
The preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving the rosin-based hyperbranched epoxy resin and the 3-aminocrotonitrile in acetone, stirring and reacting for 4 hours at 30 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain the vinyl modified rosin-based hyperbranched epoxy resin; the molar ratio of the rosin-based hyperbranched epoxy resin to the 3-aminocrotonitrile to the acetone is 1:6: 20;
step S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 6 hours at the temperature of 30 ℃, and then removing the acetone through rotary evaporation to obtain vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin; the mol ratio of the vinyl modified rosin-based hyperbranched epoxy resin to the 2-chloroethyltriethoxysilane to the acetone is 1:2: 10.
A preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: the components are mixed according to the weight part, ultrasonically dispersed for 10 minutes, and then stirred and reacted for 1 hour at the temperature of 30 ℃ to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
The application of the light-cured pressure-sensitive adhesive is characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 70mW cm-2Irradiating for 20s by ultraviolet light to obtain the pressure-sensitive adhesive product.
Example 2
The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following components in parts by weight: 17 parts of valencene myrcene/pimaric acid/trifluoroethyl acrylate copolymer, 27 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 3 parts of polyethylene glycol diacrylate, (1.5 parts of 2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 6 parts of isobornyl acrylate and 0.3 part of tris (2, 4-di-tert-butylphenyl) phosphite.
The preparation method of the valencia mandarin ene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding valencene, pimaric acid, trifluoroethyl acrylate and azodiisoheptanonitrile into N, N-dimethylformamide, stirring and reacting for 3.5 hours at 73 ℃ in the atmosphere of helium, cooling to room temperature, precipitating in water, washing the product with ethanol for 4 times, and then removing the ethanol by rotary evaporation to obtain valencene/pimaric acid/trifluoroethyl acrylate copolymer; the mass ratio of the valencia mandarin ene to the pimaric acid to the trifluoroethyl acrylate to the azodiisoheptanonitrile to the N, N-dimethylformamide is 1:1:2:0.035: 16.
The preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving the rosin-based hyperbranched epoxy resin and 3-aminocrotonitrile in toluene, stirring and reacting for 4.5 hours at 35 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain the vinyl modified rosin-based hyperbranched epoxy resin; the molar ratio of the rosin-based hyperbranched epoxy resin to the 3-aminocrotonitrile to the toluene is 1:6: 23;
step S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 6.5 hours at 33 ℃, and then performing rotary evaporation to remove the acetone to obtain vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin; the mol ratio of the vinyl modified rosin-based hyperbranched epoxy resin to the 2-chloroethyltriethoxysilane to the acetone is 1:2: 12.
A preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: the components are mixed according to the weight part, ultrasonically dispersed for 13 minutes, and then stirred and reacted for 1.5 hours at the temperature of 35 ℃ to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
The application of the light-cured pressure-sensitive adhesive is characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 75mW cm-2Irradiating the pressure-sensitive adhesive for 25s by using ultraviolet light to obtain the pressure-sensitive adhesive product.
Example 3
A weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises, by weight, 20 parts of a valencene/pimaric acid/trifluoroethyl acrylate copolymer, 30 parts of a vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 3.5 parts of polyethylene glycol diacrylate, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 7.5 parts of lauric acid acrylate and 0.4 part of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
The preparation method of the valencia mandarin ene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding bazoomyrcene, pimaric acid, trifluoroethyl acrylate and azodiisobutyronitrile into N, N-dimethylacetamide, stirring and reacting for 4 hours at 75 ℃ in the atmosphere of neon, cooling to room temperature, precipitating in water, washing a product with ethanol for 5 times, and then removing the ethanol by rotary evaporation to obtain a bazoomyrcene/pimaric acid/trifluoroethyl acrylate copolymer; the mass ratio of the valencene to the pimaric acid to the trifluoroethyl acrylate to the azodiisobutyronitrile to the N, N-dimethylacetamide is 1:1:2:0.04: 17.
The preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving the rosin-based hyperbranched epoxy resin and 3-aminocrotonitrile in tetrahydrofuran, stirring and reacting for 5 hours at 40 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain the vinyl modified rosin-based hyperbranched epoxy resin; the molar ratio of the rosin-based hyperbranched epoxy resin to the 3-aminocrotonitrile to the tetrahydrofuran is 1:6: 25;
step S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 7 hours at 35 ℃, and then removing the acetone through rotary evaporation to obtain vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin; the mol ratio of the vinyl modified rosin-based hyperbranched epoxy resin to the 2-chloroethyltriethoxysilane to the acetone is 1:2: 14.
A preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: the components are mixed according to the weight part, ultrasonically dispersed for 15 minutes, and then stirred and reacted for 2 hours at the temperature of 40 ℃ to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
The application of the light-cured pressure-sensitive adhesive is characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 80mW cm-2Irradiating the pressure-sensitive adhesive for 30s by using ultraviolet light to obtain the pressure-sensitive adhesive product.
Example 4
The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following components in parts by weight: 23 parts of a valencene myrcene/pimaric acid/trifluoroethyl acrylate copolymer, 33 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 4 parts of polyethylene glycol diacrylate, 2.5 parts of a photoinitiator, 9 parts of an active diluent and 0.5 part of an antioxidant.
The photoinitiator is prepared by mixing 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethyl benzoyl) diphenyl phosphine oxide, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and 2-isopropyl thioxanthone according to the mass ratio of 1:2:2:3, the active diluent is prepared by mixing ethoxy ethyl acrylate, isobornyl acrylate, lauric acid acrylate and tetrahydrofuran acrylate according to the mass ratio of 1:3:5:3, and the antioxidant is prepared by mixing tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite ester and β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester according to the mass ratio of 2:2:3: 2.
The preparation method of the valencia mandarin ene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding balen myrcene, pimaric acid, trifluoroethyl acrylate and an initiator into a high-boiling-point solvent, stirring and reacting for 4.5 hours at 78 ℃ in an argon atmosphere, cooling to room temperature, precipitating in water, washing the product with ethanol for 5 times, and then performing rotary evaporation to remove the ethanol to obtain a balen myrcene/pimaric acid/trifluoroethyl acrylate copolymer; the mass ratio of the valencia aurantiene to the pimaric acid to the trifluoroethyl acrylate to the initiator to the high-boiling-point solvent is 1:1:2:0.045: 18; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 2: 3; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 2:3:3: 1.
The preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving the rosin-based hyperbranched epoxy resin and the 3-aminocrotonitrile in acetone, stirring and reacting for 5.8 hours at 47 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain the vinyl modified rosin-based hyperbranched epoxy resin; the molar ratio of the rosin-based hyperbranched epoxy resin to the 3-aminocrotonitrile to the acetone is 1:6: 28;
step S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 7.5 hours at 38 ℃, and then performing rotary evaporation to remove the acetone to obtain vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin; the mol ratio of the vinyl modified rosin-based hyperbranched epoxy resin to the 2-chloroethyltriethoxysilane to the acetone is 1:2: 15.
A preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: the components are mixed according to the weight part, ultrasonically dispersed for 18 minutes, and then stirred and reacted for 2.7 hours at the temperature of 48 ℃ to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
The application of the light-cured pressure-sensitive adhesive is characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 88mW cm-2Irradiating the pressure-sensitive adhesive for 37s by using ultraviolet light to obtain the pressure-sensitive adhesive product.
Example 5
The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises, by weight, 25 parts of valencene/pimaric acid/trifluoroethyl acrylate copolymer, 35 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 5 parts of polyethylene glycol diacrylate, 3 parts of 2-isopropyl thioxanthone, 10 parts of tetrahydrofuran acrylate and 0.6 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the valencia mandarin ene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding bazoomyrcene, pimaric acid, trifluoroethyl acrylate and azodiisoheptanonitrile into N-methylpyrrolidone, stirring and reacting for 5 hours at 80 ℃ in the atmosphere of nitrogen, cooling to room temperature, precipitating in water, washing a product with ethanol for 6 times, and then performing rotary evaporation to remove the ethanol to obtain a bazoomyrcene/pimaric acid/trifluoroethyl acrylate copolymer; the mass ratio of the valencene, pimaric acid, trifluoroethyl acrylate, azodiisoheptonitrile and N-methylpyrrolidone is 1:1:2:0.05: 20.
The preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving the rosin-based hyperbranched epoxy resin and 3-aminocrotonitrile in toluene, stirring and reacting for 6 hours at 50 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain the vinyl modified rosin-based hyperbranched epoxy resin; the molar ratio of the rosin-based hyperbranched epoxy resin to the 3-aminocrotonitrile to the toluene is 1:6: 30;
step S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 8 hours at 40 ℃, and then removing the acetone through rotary evaporation to obtain vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin; the mol ratio of the vinyl modified rosin-based hyperbranched epoxy resin to the 2-chloroethyltriethoxysilane to the acetone is 1:2: 16.
A preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: the components are mixed according to the weight part, ultrasonically dispersed for 20 minutes, and then stirred and reacted for 3 hours at the temperature of 50 ℃ to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
The application of the light-cured pressure-sensitive adhesive is characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 90mW cm-2Irradiating the ultraviolet light for 40s to obtain the pressure-sensitive adhesive product.
Comparative example 1
This example provides a weatherable, water resistant photocurable pressure sensitive adhesive prepared in substantially the same manner and formulation as in example 1 except that the valencene/pimaric acid/trifluoroethyl acrylate copolymer was not added.
Comparative example 2
The present example provides a weather-resistant and water-resistant photo-curable pressure-sensitive adhesive, which has substantially the same preparation method and formula as example 1, except that a rosin-based hyperbranched epoxy resin is used to replace the vinyl cyano-group-ionized modified rosin-based hyperbranched epoxy resin.
Comparative example 3
This example provides a weatherable, water resistant, photocurable pressure sensitive adhesive prepared in substantially the same manner and formulation as in example 1, except that no polyethylene glycol diacrylate was added.
Comparative example 4
The present example provides a weather-resistant and water-resistant photo-curable pressure-sensitive adhesive, and the preparation method and the formula thereof are the same as those in example 1 of the chinese patent application No. 201711079660.3.
In order to further illustrate the beneficial technical effects of the embodiments of the present invention, the photo-curing pressure-sensitive adhesives prepared in the embodiments 1 to 5 and the comparative examples 1 to 4 are subjected to related performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) initial viscosity: testing according to GB/T4852-1984;
(2) viscosity retention: the test was performed according to GB/T4851-1998;
(3)180 ° peel strength: the test was carried out according to GB/T2792-1998.
As can be seen from table 1, the weather-resistant and water-resistant photo-curable pressure-sensitive adhesive disclosed in the examples of the present invention has a higher initial adhesion, a longer duration of the holding adhesion, and a higher peel strength, as a result of the synergistic effect of the components, compared to the photo-curable pressure-sensitive adhesive in the comparative example.
TABLE 1
| Test items | 180 degree peel force (Steel plate) | Initial adhesion | Holding power of adhesion |
| Unit of | N/25mm | # | h |
| Example 1 | 15.5 | 13 | 68 |
| Example 2 | 15.8 | 14 | 71 |
| Example 3 | 16.0 | 16 | 73 |
| Example 4 | 16.3 | 17 | 77 |
| Example 5 | 16.5 | 19 | 80 |
| Comparative example 1 | 14.1 | 9 | 53 |
| Comparative example 2 | 13.6 | 8 | 51 |
| Comparative example 3 | 14.4 | 11 | 56 |
| Comparative example 4 | 12.5 | 6 | 47 |
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: 15-25 parts of valencene myrcene/pimaric acid/trifluoroethyl acrylate copolymer, 25-35 parts of vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin, 2-5 parts of polyethylene glycol diacrylate, 1-3 parts of photoinitiator, 5-10 parts of active diluent and 0.2-0.6 part of antioxidant.
2. The photo-curable pressure-sensitive adhesive of claim 1, wherein the photo-initiator is at least one of 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-phenyl benzyl-2-dimethyl amine-1- (4-morpholine benzyl phenyl) butanone, and 2-isopropyl thioxanthone.
3. The weather-resistant and water-resistant photo-curable pressure-sensitive adhesive according to claim 1, wherein the reactive diluent is at least one of ethoxyethoxyethyl acrylate, isobornyl acrylate, lauric acid acrylate and tetrahydrofuran acrylate, and the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
4. The weather-resistant and water-resistant photo-curable pressure-sensitive adhesive according to claim 1, wherein the preparation method of the valencene/pimaric acid/trifluoroethyl acrylate copolymer comprises the following steps: adding the valencene/pimaric acid/trifluoroethyl acrylate copolymer into a high-boiling-point solvent, stirring and reacting for 3-5 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature, precipitating in water, washing the product with ethanol for 3-6 times, and then removing the ethanol by rotary evaporation to obtain the valencene/pimaric acid/trifluoroethyl acrylate copolymer.
5. The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive as claimed in claim 4, wherein the mass ratio of the valencene to the pimaric acid to the trifluoroethyl acrylate to the initiator to the high boiling point solvent is 1:1:2 (0.03-0.05) to (14-20).
6. The weather-resistant and water-resistant photo-curable pressure-sensitive adhesive according to claim 4, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
7. The weather-resistant and water-resistant photo-curable pressure-sensitive adhesive according to claim 1, wherein the preparation method of the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin comprises the following steps:
step S1, dissolving rosin-based hyperbranched epoxy resin and 3-aminocrotonitrile in an organic solvent, stirring and reacting for 4-6 hours at 30-50 ℃ under the action of oxygen inhibition, and then removing the solvent by rotary evaporation to obtain vinyl modified rosin-based hyperbranched epoxy resin;
and S2, adding the vinyl modified rosin-based hyperbranched epoxy resin prepared in the step S1 and 2-chloroethyltriethoxysilane into acetone, stirring and reacting for 6-8 hours at the temperature of 30-40 ℃, and then performing rotary evaporation to remove the acetone to obtain the vinyl cyano-ionized modified rosin-based hyperbranched epoxy resin.
8. The weather-resistant and water-resistant photo-curable pressure-sensitive adhesive according to claim 7, wherein the molar ratio of the rosin-based hyperbranched epoxy resin, the 3-aminocrotonitrile and the organic solvent in the step S1 is 1:6 (20-30); the organic solvent is any one of acetone, toluene and tetrahydrofuran; the molar ratio of the vinyl modified rosin-based hyperbranched epoxy resin, the 2-chloroethyltriethoxysilane and the acetone in the step S2 is 1:2 (10-16).
9. The weather-resistant and water-resistant photo-curing pressure-sensitive adhesive according to any one of claims 1 to 8, wherein the preparation method of the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive comprises the following steps: mixing the components in parts by weight, performing ultrasonic dispersion for 10-20 minutes, and then stirring and reacting at 30-50 ℃ for 1-3 hours to obtain the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive.
10. The weather-resistant and water-resistant photocurable pressure-sensitive adhesive according to any one of claims 1-8, characterized in that: uniformly coating the weather-resistant and water-resistant photo-curing pressure-sensitive adhesive on a base material, wherein the radiation dose is 70-90mW cm-2Irradiating by ultraviolet light for 20-40 s to obtain the pressure-sensitive adhesive product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406863A (en) * | 2021-06-16 | 2021-09-17 | 田菱智能科技(昆山)有限公司 | Photo-thermal dual-curing photosensitive glue, and preparation method and application method thereof |
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2020
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406863A (en) * | 2021-06-16 | 2021-09-17 | 田菱智能科技(昆山)有限公司 | Photo-thermal dual-curing photosensitive glue, and preparation method and application method thereof |
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