CN103589264B - A kind of UV-curable water-borne acrylic ester polymer coating and preparation method thereof - Google Patents
A kind of UV-curable water-borne acrylic ester polymer coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to Water-borne Acrylic Coating field, disclose a kind of BOPP UV-curable water-borne acrylic ester polymer coating and its preparation method and application.This coating comprises acrylic ester prepolymer and light trigger.Introduce oxyethyl group in the acrylic ester prepolymer of BOPP UV-curable water-borne acrylic ester polymer coating of the present invention, there is lower shrinking percentage, preferably snappiness and mobility; Water-based group in structure, after can making film forming, polarity is less, ensures the spreadability of water-borne coatings, and the pollution of avoiding with an organic solvent dissolving prepolymer and causing and harm; Introducing can carry out the reactive group of ultraviolet light polymerization, irradiation post-consumer polymer through UV-light occurs crosslinked, can when not adding small molecules auxiliary agent the force of cohesion of effective raising system, increase the service life, efficiently, energy-saving and environmental protection, both can be used as coating, and also can be used as binding agent and use, be conducive to the application of BOPP film in fields such as printing, bags.
Description
Technical field
The invention belongs to Water-borne Acrylic Coating field, particularly a kind of BOPP UV-curable water-borne acrylic ester polymer coating and its preparation method and application.
Background technology
Biaxially oriented polypropylene film (BOPP) (BOPP) thin film have colourless, tasteless, nontoxic, transparency is high, tensile strength is high, shock strength high, is widely used in the fields such as food, clothes, medicine, chemical industry, is the very fast a kind of wrapping material of development in recent years.Have stiff molecule chain in BOPP, and polar group is few, causes that its polarity is little, surface energy is low, use the solvent that water isopolarity is large in environmental protection coating material, cause the bonding properties of coating resin and film very poor.UV-curing technology utilizes light trigger under UV-irradiation, cause that unsaturated monomer carries out being polymerized, grafting, the chemical reaction such as crosslinked thus reach a kind of emerging technology of rapid solidification.Owing to having the features such as set time is short, equipment is simple, capacity usage ratio is high, solidification value is low, free from environmental pollution, be widely used in the fields such as coating, tamanori and ink.Because solvent based coating is better to the bonding properties of material, generally use solvent-borne type ultraviolet-curing paint at present, but organic solvent there is potential safety hazard, contaminate environment.In order to reduce the viscosity of photocuring system, increase the force of cohesion of mobility and increase solidify material, usually add reactive thinner in system, but reactive thinner can be irritant to the skin of people, mucous membrane and eyes; Photocuring system is radical photopolymerization mainly, because of oxygen inhibition, polymerization not exclusively, still residual activity thinner in solidified coating, therefore traditional photo-curing material is unsuitable for printing and the application of the wrapping material of food sanitation product.Due to the existence of small molecules thinner, the volumetric shrinkage of the material in solidification process is comparatively large, causes ultraviolet-curing paint effectively not play a role.Being used for the coating apparatus of coated UV curable coating and container needs organic solvent cleaning, causes disadvantageous effect to the health of producers.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of BOPP UV-curable water-borne acrylic ester polymer coating.Introduce oxyethyl group in (methyl) acrylic ester prepolymer in coating of the present invention, there is lower shrinking percentage, preferably snappiness and mobility; Water-based group appropriate in structure, after can making film forming, polarity is less, ensures the spreadability of water-borne coatings on BOPP plastics film, and the pollution of avoiding with an organic solvent dissolving prepolymer and causing and harm; Introducing can carry out the reactive group of ultraviolet light polymerization, makes can carry out ultraviolet light polymerization containing unsaturated carbon-carbon double bond in the system obtained.
Another object of the present invention is the preparation method providing a kind of above-mentioned BOPP UV-curable water-borne acrylic ester polymer coating.
Still a further object of the present invention is the application providing above-mentioned BOPP UV-curable water-borne acrylic ester polymer coating as binding agent.
Object of the present invention is realized by following proposal:
A kind of BOPP UV-curable water-borne acrylic ester polymer coating, comprises acrylic ester prepolymer and light trigger.
Described acrylic ester prepolymer has following structure:
Wherein, R is H or CH
3, n=1 ~ 6, x
1=1 ~ 250, x
2=1 ~ 500, y=50 ~ 500, z=2 ~ 500.
The mass ratio of described light trigger and acrylic ester prepolymer is (1 ~ 5): 100.
Described light trigger refers to α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl phenyl-2-hydroxy-2-methyl acetone, 1-hydroxy-cyciohexyl benzophenone, 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2, at least one in 4,6-trimethylbenzoyl diethyl phosphonate and benzophenone.
A preparation method for above-mentioned BOPP UV-curable water-borne acrylic ester polymer coating, comprises the following steps:
(methyl) vinylformic acid, ethoxyethoxyethyl acrylate, (methyl) alkyl acrylate, part initiator are mixed, reacting by heating, then add residue initiator continuation reaction; Add catalyzer, stopper, (methyl) glycidyl acrylate, after temperature reaction, with basic solution neutralization, obtain acrylic ester prepolymer; Add light trigger, obtain BOPP UV-curable water-borne acrylic ester polymer coating.
Described (methyl) alkyl acrylate refers at least one in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, isoamyl acrylate and (methyl) Ethyl acrylate.
Described initiator refers at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo dicyclohexyl formonitrile HCN.
Described catalyzer refers at least one in Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, benzyl triethyl ammonium bromide, bromination tributyl benzylamine, trioctylphosphine brometo de amonio, tri-n-octyl methyl ammonium chloride and 4-butyl ammonium fluoroborate.
Described stopper refers at least one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone and 2,5 di tert butyl hydroquinone.
The mass ratio of (methyl) used vinylformic acid, ethoxyethoxyethyl acrylate, (methyl) alkyl acrylate, initiator, catalyzer, stopper and (methyl) glycidyl acrylate is (10 ~ 40): (50 ~ 80): (10 ~ 30): (3 ~ 4): (0.5 ~ 1): (0.2 ~ 0.5): (5 ~ 20).
The amount of described part initiator accounts for 60 ~ 75% of initiator total mass.
Described reacting by heating refers to 500 ~ 1000r/min stirring reaction 0.5h at 75 ~ 80 DEG C.
Preferably, described reacting by heating is carried out in the environment of logical nitrogen.
Described continuation reaction refers to reaction 10 ~ 15h.
Described temperature reaction refers at 102 ~ 110 DEG C of reaction 4 ~ 5h.
The mass ratio of basic solution used and acrylic ester prepolymer is (5 ~ 10): 100.
Described basic solution prepares by 2 ~ 5 weight part alkaline reagentss are dissolved in 10 weight parts waters.
Described alkaline reagents refers at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide and ammoniacal liquor.
Above-mentioned BOPP UV-curable water-borne acrylic ester polymer coating, as the application of binding agent, is realized by following methods:
BOPP with UV-curable water-borne acrylic ester polymer paint on BOPP, after air-dry, be placed in place under ultraviolet lamp and irradiate solidification.
The wavelength region of described ultraviolet lamp is 200 ~ 400nm.
Mechanism of the present invention is:
The present invention, by introducing oxyethyl group in acrylic ester prepolymer side chain, makes acrylic ester prepolymer have lower shrinking percentage, preferably snappiness and mobility, is conducive to prepolymer sprawling on BOPP film surface; Water-based group appropriate in structure, can make the polarity of prepolymer after BOPP surface filming less, ensures the spreadability of water-borne coatings on BOPP plastics film; In the side chain of acrylic ester prepolymer, also introduce the reactive group that can carry out ultraviolet light polymerization simultaneously, make to contain unsaturated carbon-carbon double bond in the system obtained to carry out ultraviolet light polymerization, irradiation post-consumer polymer through UV-light occurs crosslinked, can when not adding small molecules auxiliary agent the force of cohesion of effective raising system, increase the service life.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention is by the kind of adjustment synthon, can obtain a series of BOPP UV-curable water-borne acrylic ester polymer coating through reaction.
(2) introduce oxyethyl group in the acrylic ester prepolymer of BOPP UV-curable water-borne acrylic ester polymer coating of the present invention, there is lower shrinking percentage, preferably snappiness and mobility; Water-based group appropriate in structure, after can making film forming, polarity is less, ensures the spreadability of water-borne coatings on BOPP plastics film, and the pollution of avoiding with an organic solvent dissolving prepolymer and causing and harm.
(3) reactive group that can carry out ultraviolet light polymerization is introduced in the acrylic ester prepolymer of BOPP UV-curable water-borne acrylic ester polymer coating of the present invention, make to contain unsaturated carbon-carbon double bond in the system obtained to carry out ultraviolet light polymerization, irradiation post-consumer polymer through UV-light occurs crosslinked, can when not adding small molecules auxiliary agent the force of cohesion of effective raising system, increase the service life, efficiently, energy-saving and environmental protection, effectively can improve production rate.
(4) Polypropylene structural of BOPP UV-curable water-borne acrylic ester polymer backbone of the present invention and BOPP has similarity, and the acrylic ester polymer coating used as coating and BOPP film have good sticking power; As binding agent use, can effectively by BOPP film together with the material binding of opposed polarity, be conducive to the application of BOPP film in fields such as printing, bags.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the free radical polyalcohol for preparing of embodiment 1 and acrylic ester prepolymer M1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In the following example, each performance test is according to following standard:
The volumetric shrinkage of polymer coating: measure by ISO3521;
The shearing resistance of polymer coating: measure by GB/T7124;
The annular initial adhesive strength of polymer coating: measure by FINATFTM9-2003;
180 ° of stripping strengths of polymer coating: measure by GB/2792-1998;
Polymer coating hold viscosity: measure by GB/4851-1998.
The embodiment 1:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add 40 parts, vinylformic acid, ethoxyethoxyethyl acrylate 50 parts, methyl acrylate 10, Diisopropyl azodicarboxylate 2 parts successively, be stirred to the rotating speed machinery of 500r/min in the environment of logical nitrogen and mix, be warming up to 75 DEG C, reaction 0.5h, then add Diisopropyl azodicarboxylate 1 part, after continuing reaction 10h, obtain free radical polyalcohol; Add the Tetrabutyl amonium bromide of 0.5 part again, the hydroquinone of polymerization retarder of 0.2 part, glycidyl acrylate 5 parts, be warming up to 102 DEG C of reaction 4h; The sodium hydroxide of 2 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 5 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N1;
Infrared spectrum analysis is carried out to acrylic ester prepolymer before the free radical polyalcohol obtained in building-up process and neutralization, the results are shown in Figure 1, as seen from the figure, 1630cm in free radical polyalcohol
-1the C=C stretching vibration peak at place disappears, and shows to successfully synthesize radical polymerization product; The 1630cm of acrylic ester prepolymer
-1there is C=C stretching vibration peak in place, and 3500cm
-1having there is wider peak in place, carboxyl is described successfully by epoxy ring-opening, introduces photoactive double bond.
(2) in the acrylic ester prepolymer N1 of gained, 1 part of α is added, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.58%, shearing resistance 4.01 × 10
5pa, annular initial bonding strength 7.91N/25mm, 180 ° of stripping strengths are 7.62N/25mm, hold sticky 2.90h.
The embodiment 2:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add 10 parts, vinylformic acid, ethoxyethoxyethyl acrylate 80 parts, ethyl propenoate 10 parts, 2,2'-Azobis(2,4-dimethylvaleronitrile) 3 parts successively, be stirred to the rotating speed machinery of 1000r/min in the environment of logical nitrogen and mix, be warming up to 80 DEG C, reaction 0.5h, then add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part, after continuing reaction 15h; Add the tetrabutylammonium chloride of 1 part again, the para benzoquinone of 0.5 part, glycidyl acrylate 5 parts, be warming up to 110 DEG C of reaction 5h; The sodium hydroxide of 5 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 5 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N2;
(2) 5 parts of α can be added in the acrylic ester prepolymer N2 of UV photocuring at gained, α-diethoxy acetophenone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.57%, shearing resistance 4.06 × 10
5pa, annular initial bonding strength 7.89N/25mm, 180 ° of stripping strengths are 7.63N/25mm, hold sticky 2.89h.
The embodiment 3:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add 20 parts, vinylformic acid, ethoxyethoxyethyl acrylate 50 parts, propyl acrylate 30 parts, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.5 parts successively, be stirred to the rotating speed machinery of 700r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, then add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part, after continuing reaction 12h; Add the 4-butyl ammonium hydrogen sulfate of 0.6 part again, the toluhydroquinone of 0.3 part, glycidyl acrylate 10 parts, be warming up to 105 DEG C of reaction 4.5h; The potassium hydroxide of 2 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 10 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N3;
(2) 4 parts of 2-hydroxyl-2 methyl isophthalic acids-phenyl-1-acetone can be added in the acrylic ester prepolymer N3 of UV photocuring at gained, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.58%, shearing resistance 4.05 × 10
5pa, annular initial bonding strength 7.92N/25mm, 180 ° of stripping strengths are 7.62N/25mm, hold sticky 2.87h.
The embodiment 4:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add 20 parts, vinylformic acid, ethoxyethoxyethyl acrylate 60 parts, butyl acrylate 20 parts, azo dicyclohexyl formonitrile HCN 2.5 parts successively, be stirred to the rotating speed machinery of 600r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, then add azo dicyclohexyl formonitrile HCN 1 part, after continuing reaction 13h; Add the benzyl triethyl ammonium bromide of 0.8 part again, the MEHQ of 0.4 part, glycidyl acrylate 16 parts, be warming up to 105 DEG C of reaction 4h; The sodium hydroxide of 3 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 8 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N4;
(2) 3 parts of isopropyl phenyl-2-hydroxy-2-methyl acetone can be added in the acrylic ester prepolymer N4 of UV photocuring at gained, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.56%, shearing resistance 4.03 × 10
5pa, annular initial bonding strength 7.90N/25mm, 180 ° of stripping strengths are 7.64N/25mm, hold sticky 2.89h.
The embodiment 5:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 40 parts, ethoxyethoxyethyl acrylate 50 parts, methyl methacrylate 10 parts, Diisopropyl azodicarboxylate 2 parts successively, be stirred to the rotating speed machinery of 800r/min in the environment of logical nitrogen and mix, be warming up to 75 DEG C, reaction 0.5h, then add Diisopropyl azodicarboxylate 1 part, after continuing reaction 10h; Add the bromination tributyl benzylamine of 0.5 part again, the 2-Tert. Butyl Hydroquinone of 0.2 part, glycidyl methacrylate 12 parts, be warming up to 106 DEG C of reaction 5h; The sodium hydroxide of 4 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 6 parts and above-mentioned reaction system, obtain methacrylate prepolymers N5;
(2) 1 part of 1-hydroxy-cyciohexyl benzophenone can be added in the methacrylate prepolymers N5 of UV photocuring at gained, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 400nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.59%, shearing resistance 4.02 × 10
5pa, annular initial bonding strength 7.92N/25mm, 180 ° of stripping strengths are 7.67N/25mm, hold sticky 2.90h.
The embodiment 6:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 10 parts, ethoxyethoxyethyl acrylate 80 parts, β-dimethyl-aminoethylmethacrylate 10 parts, initiator 3 parts successively, be stirred to the rotating speed machinery of 900r/min in the environment of logical nitrogen and mix, be warming up to 80 DEG C, reaction 0.5h, then add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part, after continuing reaction 15h; Add the trioctylphosphine brometo de amonio of 1 part, the 2,5 di tert butyl hydroquinone of 0.5 part, glycidyl methacrylate 6 parts, be warming up to 108 DEG C of reaction 5h; The sodium hydroxide of 2 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 10 parts and above-mentioned reaction system, obtain methacrylate prepolymers N6;
(2) 5 parts of 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone can be added in the methacrylate prepolymers N6 of UV photocuring at gained, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 200nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.60%, shearing resistance 4.01 × 10
5pa, annular initial bonding strength 7.93N/25mm, 180 ° of stripping strengths are 7.65N/25mm, hold sticky 2.87h.
The embodiment 7:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 20 parts, ethoxyethoxyethyl acrylate 50 parts, butyl methacrylate 30 parts, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.5 parts successively, be stirred to the rotating speed machinery of 500r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, then add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part, after continuing reaction 12h; Add the 4-butyl ammonium fluoroborate of 0.6 part again, the Resorcinol of 0.3 part, glycidyl methacrylate 15 parts, be warming up to 103 DEG C of reaction 4.5h; The sodium hydroxide of 5 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 7 parts and above-mentioned reaction system, obtain methacrylate prepolymers N7;
(2) 4 parts of 2-phenyl-2 can be added in the methacrylate prepolymers N7 of UV photocuring at gained, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.57%, shearing resistance 4.02 × 10
5pa, annular initial bonding strength 7.91N/25mm, 180 ° of stripping strengths are 7.64N/25mm, hold sticky 2.89h.
The embodiment 8:BOPP preparation of UV-curable water-borne acrylic ester polymer coating
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 20 parts, ethoxyethoxyethyl acrylate 60 parts, N-Hexyl methacrylate 20 parts, azo dicyclohexyl formonitrile HCN 2.5 parts successively, be stirred to the rotating speed machinery of 600r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, then add azo dicyclohexyl formonitrile HCN 1 part, after continuing reaction 13h; Add the tri-n-octyl methyl ammonium chloride of 0.8 part again, the 2-Tert. Butyl Hydroquinone of 0.4 part, glycidyl methacrylate 16 parts, be warming up to 104 DEG C of reaction 4h; The sodium hydroxide of 4 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 8 parts and above-mentioned reaction system, obtain methacrylate prepolymers N8;
(2) 3 part 2 can be added in the methacrylate prepolymers N8 of UV photocuring at gained, 4,6-trimethylbenzoyl diethyl phosphonate, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, to be placed on the ultraviolet lamp 4cm place that distance wavelength is 365nm after moisture volatilizees completely, it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.57%, shearing resistance 4.03 × 10
5pa, annular initial bonding strength 7.92N/25mm, 180 ° of stripping strengths are 7.62N/25mm, hold sticky 2.90h.
Comparative example 1: not containing the preparation of the acrylic ester polymer coating of optical active group
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 20 parts, ethoxyethoxyethyl acrylate 50 parts, butyl methacrylate 30 parts, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.5 parts successively, be stirred to the rotating speed machinery of 500r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, then add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part, after continuing reaction 12h; The sodium hydroxide of 5 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 7 parts and above-mentioned reaction system, obtain not containing the acrylic ester prepolymer N9 of optical active group;
(2) the acrylic ester prepolymer N9 not containing optical active group of gained is coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 1.48%, shearing resistance 3.26 × 10
5pa, annular initial bonding strength 7.89N/25mm, 180 ° of stripping strengths are 7.03N/25mm, hold sticky 2.54h.
Comparative example 2: not containing the preparation of the acrylic ester polymer of ethoxy side chain
(1) by weight, in the reactor with agitator, prolong, add methacrylic acid 20 parts, N-Hexyl methacrylate 50 parts, butyl methacrylate 30 parts, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.5 parts successively, be stirred to the rotating speed machinery of 500r/min in the environment of logical nitrogen and mix, be warming up to 78 DEG C, reaction 0.5h, add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1 part again, after continuing reaction 12h, add the 4-butyl ammonium fluoroborate of 0.6 part, the Resorcinol of 0.3 part, glycidyl methacrylate 15 parts, is warming up to 103 DEG C of reaction 4.5h; The sodium hydroxide of 5 parts is joined in 10 parts of deionized waters, be made into basic solution; With in the basic solutions of 7 parts and above-mentioned reaction system, obtained not containing the acrylic ester prepolymer N10 of ethoxy side chain;
(2) 3 parts of benzophenone are added in not containing in the acrylic ester prepolymer T2 of ethoxy side chain of gained, mix, and be coated with the thick film of 0.08mm at BOPP film surface, to be placed in stink cupboard 1 hour, being placed on distance wavelength after moisture volatilizees completely is the ultraviolet lamp 4cm place of 365nm, and it is as follows to irradiate performance after 5 seconds:
Volumetric shrinkage 3.12%, shearing resistance 4.04 × 10
5pa, annular initial bonding strength 7.61N/25mm, 180 ° of stripping strengths are 7.66N/25mm, hold sticky 2.88h.
By the curing performance of the UV light-cured acrylate polymer coating of embodiment and comparative example, the acrylic ester polymer adopting different monomers to obtain has different volumetric shrinkages, shearing resistance, annular initial adhesive strength, 180 ° of stripping strengths and holds viscosity after ultraviolet light polymerization.From the performance of comparative example 1, use and there is not ultraviolet curing group polymer-coated when BOPP film surface is tested, because force of cohesion is not enough, the adhesive property index recorded is lower than the index of polymkeric substance photo curable in embodiment; From the performance test results of comparative example 2, use containing the acrylic ester polymer of ethoxy side chain be coated in BOPP film surface test time, because mobility is not good enough, segment is easily frozen in the curing process, adhesive property is not good enough, and the volumetric shrinkage of acrylic ester polymer coating is comparatively large, the volumetric shrinkage of the acrylic ester polymer coating containing ethoxy side chain in embodiment drops to less than 2%, shearing resistance and hold the performances such as sticky time and be improved.
As can be seen here, the BOPP UV-curable water-borne acrylic ester polymer coating that the present invention relates to, owing to introducing oxyethyl group in acrylic ester prepolymer side chain, acrylic ester prepolymer can be made to have lower shrinking percentage, preferably snappiness and mobility, be conducive to prepolymer sprawling on BOPP film surface; Water-based group appropriate in structure, the water-borne coatings of the environmental protection that can be made into; Introduce in the side chain of acrylic ester prepolymer and can carry out the reactive group of ultraviolet light polymerization, can when not adding small molecules auxiliary agent the force of cohesion of effective raising system, increase the service life, energy-conserving and environment-protective.The backbone of acrylate and the Polypropylene structural of BOPP have similarity, and the acrylic ester polymer used as coating and BOPP film have good sticking power.Use this acrylic ester prepolymer as the main component of binding agent, can effectively by BOPP film together with the material binding of opposed polarity, be conducive to the application of BOPP film in fields such as printing, bags, thus reach the technology of the present invention improve effect.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a UV-curable water-borne acrylic ester polymer coating, is characterized in that: comprise acrylic ester prepolymer and light trigger;
Described acrylic ester prepolymer has following structure:
Wherein, R is H or CH
3, n=1 ~ 6, x
1=1 ~ 250, x
2=1 ~ 500, y=50 ~ 500, z=2 ~ 500;
Described UV-curable water-borne acrylic ester polymer coating is prepared by the method for comprising the following steps:
(methyl) vinylformic acid, ethoxyethoxyethyl acrylate, (methyl) alkyl acrylate, part initiator are mixed, reacting by heating, then add residue initiator continuation reaction; Add catalyzer, stopper, (methyl) glycidyl acrylate, temperature reaction, obtains acrylic ester prepolymer M; With in basic solution and acrylic ester prepolymer M, obtain acrylic ester prepolymer N; Add light trigger, obtain BOPP UV-curable water-borne acrylic ester polymer coating.
2. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: the mass ratio of described light trigger and acrylic ester prepolymer is (1 ~ 5): 100.
3. UV-curable water-borne acrylic ester polymer coating according to claim 1, it is characterized in that: described light trigger refers to α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl phenyl-2-hydroxy-2-methyl acetone, 1-hydroxy-cyciohexyl benzophenone, 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2-phenyl-2, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2, 4, at least one in 6-trimethylbenzoyl diethyl phosphonate and benzophenone.
4. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: described (methyl) alkyl acrylate refers at least one in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, isoamyl acrylate and (methyl) Ethyl acrylate.
5. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: described initiator refers at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo dicyclohexyl formonitrile HCN; Described catalyzer refers at least one in Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, benzyl triethyl ammonium bromide, bromination tributyl benzylamine, trioctylphosphine brometo de amonio, tri-n-octyl methyl ammonium chloride and 4-butyl ammonium fluoroborate; Described stopper refers at least one in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone and 2,5 di tert butyl hydroquinone.
6. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: the mass ratio of (methyl) used vinylformic acid, ethoxyethoxyethyl acrylate, (methyl) alkyl acrylate, initiator, catalyzer, stopper and (methyl) glycidyl acrylate is (10 ~ 40): (50 ~ 80): (10 ~ 30): (3 ~ 4): (0.5 ~ 1): (0.2 ~ 0.5): (5 ~ 20); The amount of described part initiator accounts for 60 ~ 75% of initiator total mass.
7. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: described reacting by heating refers to 500 ~ 1000r/min stirring reaction 0.5h at 75 ~ 80 DEG C; Described reacting by heating is carried out in the environment of logical nitrogen; Described continuation reaction refers to reaction 10 ~ 15h; Described temperature reaction refers at 102 ~ 110 DEG C of reaction 4 ~ 5h; The mass ratio of basic solution used and acrylic ester prepolymer M is (5 ~ 10): 100.
8. UV-curable water-borne acrylic ester polymer coating according to claim 1, is characterized in that: described basic solution prepares by 2 ~ 5 weight part alkaline reagentss are dissolved in 10 weight parts waters; Described alkaline reagents refers at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide and ammoniacal liquor.
9. the UV-curable water-borne acrylic ester polymer coating according to any one of claims 1 to 3, as the application of binding agent, is characterized in that being realized by following methods:
BOPP with UV-curable water-borne acrylic ester polymer paint on BOPP, after air-dry, be placed in place under ultraviolet lamp and irradiate solidification; The wavelength region of described ultraviolet lamp is 200 ~ 400nm.
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| CN103059315A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Polyurethane/polyacrylate copolymer and BOPP (Biaxially-oriented Polypropylene) film prepared by same |
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| CN103059315A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Polyurethane/polyacrylate copolymer and BOPP (Biaxially-oriented Polypropylene) film prepared by same |
| CN103059316A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Polyurethane/polyacrylate copolymer modified by organic fluoride and ultraviolet curing coating prepared by polyurethane/polyacrylate copolymer |
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