CN103589264A - Ultraviolet light cured aqueous acrylate polymer coating and preparation method thereof - Google Patents
Ultraviolet light cured aqueous acrylate polymer coating and preparation method thereof Download PDFInfo
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- CN103589264A CN103589264A CN201310513772.0A CN201310513772A CN103589264A CN 103589264 A CN103589264 A CN 103589264A CN 201310513772 A CN201310513772 A CN 201310513772A CN 103589264 A CN103589264 A CN 103589264A
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Abstract
The invention belongs to the field of aqueous acrylate coatings, and discloses an ultraviolet light cured aqueous acrylate polymer coating for BOPP, and a preparation method and an application thereof. The coating includes an acrylate prepolymer and a photoinitiator. The acrylate prepolymer of the ultraviolet light cured aqueous acrylate polymer coating for BOPP is introduced with an ethoxy group, so the coating has a low shrinkage, a good flexibility and a good fluidity; an aqueous group in the structure enables the polarity of a film formed by the coating to be small, guarantees the spreadability of the aqueous coating, and avoids the pollution and harms caused by the use of an organic solvent to dissolve the prepolymer; and a responsive group which can be cured by ultraviolet light is introduced, and the polymer crosslinks after the ultraviolet light irradiation, so the cohesive force of a system is effectively improved without adding a micro-molecular assistant, the service life is prolonged, and high-efficiency, energy-saving and environmental-protection are realized; the polymer can be used as a coating, can also be used as a binder, is in favor of application of a BOPP film in the printing and bag making fields.
Description
Technical field
The invention belongs to Water-borne Acrylic Coating field, particularly UV-curable water-borne acrylic ester polymer coating and its preparation method and application for a kind of BOPP.
Background technology
That Biaxially oriented polypropylene film (BOPP) (BOPP) film has is 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.In BOPP, have stiff molecule chain, and polar group is few, causes its polarity little, surface can be low, uses the solvent that water isopolarity is large in environmental protection coating material, causes the bonding properties of coating resin and film very poor.UV-curing technology is to utilize light trigger under UV-irradiation, thereby cause, unsaturated monomer carries out polymerization, grafting, the chemical reaction such as crosslinked reaches a kind of emerging technology of solidifying rapidly.Owing to thering is 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 at present solvent-borne type ultraviolet-curing paint, but organic solvent there is potential safety hazard, contaminate environment.In order to reduce the force of cohesion of viscosity, increase mobility and the increase solidify material of photocuring system, in system, conventionally add reactive thinner, but reactive thinner can be irritant to people's skin, mucous membrane and eyes; Photocuring system is mainly radical photopolymerization, and because of oxygen inhibition, polymerization is incomplete, and residual activity thinner still 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 larger, causes ultraviolet-curing paint effectively not play a role.The coating apparatus and the container that are used for being coated with ultraviolet-curing paint need organic solvent to clean, and producers' health is caused to disadvantageous effect.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide UV-curable water-borne acrylic ester polymer coating for a kind of BOPP.In (methyl) acrylic ester prepolymer in coating of the present invention, introduce oxyethyl group, there is lower shrinking percentage, good snappiness and mobility; Appropriate water-based group in structure, can make film forming after polarity less, guarantee the spreadability of water-borne coatings on BOPP plastics film, and avoid with an organic solvent dissolving prepolymer and the pollution and the harm that cause; Introducing can be carried out the reactive group of ultraviolet light polymerization, contains unsaturated carbon-carbon double bond and can carry out ultraviolet light polymerization in the system that makes to obtain.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned BOPP with UV-curable water-borne acrylic ester polymer coating.
Still a further object of the present invention is to provide above-mentioned BOPP application as binding agent with UV-curable water-borne acrylic ester polymer coating.
Object of the present invention realizes by following proposal:
With a UV-curable water-borne acrylic ester polymer coating, 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.
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 methyl phenyl ketone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl phenyl-2-hydroxy-2-methyl acetone, 1-hydroxyl-phenylcyclohexyl ketone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2, at least one in 4,6-Three methyl Benzene formyl diethyl phosphonate and benzophenone.
A preparation method for UV-curable water-borne acrylic ester polymer coating for above-mentioned BOPP, comprises the following steps:
(methyl) vinylformic acid, ethoxy ethoxy ethyl propylene acid esters, (methyl) alkyl acrylate, part initiator are mixed, reacting by heating, then add residue initiator to continue reaction; Add catalyzer, stopper, (methyl) glycidyl acrylate, after temperature reaction, with basic solution neutralization, obtains acrylic ester prepolymer; Add light trigger, obtain UV-curable water-borne acrylic ester polymer coating for BOPP.
Described (methyl) alkyl acrylate refers at least one in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, vinylformic acid isopentyl ester 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, ethoxy ethoxy ethyl propylene acid esters, (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 ℃.
Preferably, described reacting by heating is carried out in the environment of logical nitrogen.
Described continuation reaction refers to react 10～15h.
Described temperature reaction refers at 102～110 ℃ of reaction 4～5h.
The mass ratio of basic solution used and acrylic ester prepolymer is (5～10): 100.
Described basic solution is by being dissolved in 2～5 weight part alkaline reagentss in 10 weight parts waters and preparing.
Described alkaline reagents refers at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide and ammoniacal liquor.
Above-mentioned BOPP is the application as binding agent with UV-curable water-borne acrylic ester polymer coating, by following methods, is realized:
BOPP is coated in to BOPP with UV-curable water-borne acrylic ester polymer coating upper, air-dry after, be placed in to locate to irradiate under ultraviolet lamp and solidify.
The wavelength region of described ultraviolet lamp is 200～400nm.
Mechanism of the present invention is:
The present invention, by introduce oxyethyl group in acrylic ester prepolymer side chain, makes acrylic ester prepolymer have lower shrinking percentage, good snappiness and mobility, is conducive to prepolymer sprawling on BOPP film surface; Appropriate water-based group in structure, can make the polarity of prepolymer after BOPP surface filming less, guarantees the spreadability of water-borne coatings on BOPP plastics film; Also in the side chain of acrylic ester prepolymer, introduce the reactive group that can carry out ultraviolet light polymerization simultaneously, in the system that makes to obtain, contain unsaturated carbon-carbon double bond to carry out ultraviolet light polymerization, irradiation post polymerization thing through UV-light occurs crosslinked, can be in the situation that not adding small molecules auxiliary agent the effective force of cohesion of raising system, increase the service life.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention, by adjusting the kind of synthon, can obtain UV-curable water-borne acrylic ester polymer coating for a series of BOPP through reaction.
(2) in the acrylic ester prepolymer of BOPP of the present invention with UV-curable water-borne acrylic ester polymer coating, introduce oxyethyl group, there is lower shrinking percentage, good snappiness and mobility; Appropriate water-based group in structure, can make film forming after polarity less, guarantee the spreadability of water-borne coatings on BOPP plastics film, and avoid with an organic solvent dissolving prepolymer and the pollution and the harm that cause.
(3) BOPP of the present invention is with introducing the reactive group that can carry out ultraviolet light polymerization in the acrylic ester prepolymer of UV-curable water-borne acrylic ester polymer coating, in the system that makes to obtain, contain unsaturated carbon-carbon double bond to carry out ultraviolet light polymerization, irradiation post polymerization thing through UV-light occurs crosslinked, can be in the situation that not adding small molecules auxiliary agent the effective force of cohesion of raising system, increase the service life, efficiently, energy-saving and environmental protection, can effectively improve production rate.
(4) BOPP of the present invention has similarity by the polypropylene structure of UV-curable water-borne acrylic ester polymer backbone and BOPP, and the acrylic ester polymer coating and the BOPP film that as coating, use have good sticking power; As binding agent, use, can be effectively by together with the material binding of BOPP film and opposed polarity, be conducive to BOPP film in the application in the fields such as printing, bag.
Accompanying drawing explanation
Fig. 1 is the free radical polyalcohol for preparing of embodiment 1 and the infrared spectrum of 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 to this.
In the following example, each performance test is according to following standard:
The volumetric shrinkage of polymer coating: press ISO3521 and measure;
The shearing resistance of polymer coating: press GB/T7124 and measure;
The annular initial adhesive strength of polymer coating: press FINAT FTM9-2003 and measure;
180 ° of stripping strengths of polymer coating: press GB/2792-1998 and measure;
Polymer coating hold viscosity: by GB/4851-1998, measure.
The preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 1:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 2 parts, 40 parts, vinylformic acid, 50 parts of ethoxy ethoxy ethyl propylene acid esters, methyl acrylate 10, Diisopropyl azodicarboxylate, in the environment of logical nitrogen, with the rotating speed machinery of 500r/min, be stirred to and mix, be warming up to 75 ℃, reaction 0.5h, then add 1 part of Diisopropyl azodicarboxylate, continue, after reaction 10h, to obtain free radical polyalcohol; The Tetrabutyl amonium bromide that adds again 0.5 part, the hydroquinone of polymerization retarder of 0.2 part, 5 parts of glycidyl acrylates, are warming up to 102 ℃ 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 solution of 5 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N1;
Acrylic ester prepolymer before the free radical polyalcohol obtaining in building-up process and neutralization is carried out to infrared spectrum analysis, 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, illustrates that carboxyl is successfully by epoxy ring-opening, introduced photoactive pair of key.
(2) in the acrylic ester prepolymer N1 of gained, add 1 part of α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 2:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 10 parts, vinylformic acid, 80 parts of ethoxy ethoxy ethyl propylene acid esters, 10 parts of ethyl propenoates, 3 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), in the environment of logical nitrogen, with the rotating speed machinery of 1000r/min, be stirred to and mix, be warming up to 80 ℃, reaction 0.5h, then add 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after reaction 15h; The tetrabutylammonium chloride that adds again 1 part, the para benzoquinone of 0.5 part, 5 parts of glycidyl acrylates, are warming up to 110 ℃ 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 solution of 5 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N2;
(2) at gained, can in the acrylic ester prepolymer N2 of UV photocuring, add 5 parts of α, α-diethoxy acetophenone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 3:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts, vinylformic acid, 50 parts of ethoxy ethoxy ethyl propylene acid esters, 30 parts of propyl acrylates, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), in the environment of logical nitrogen, with the rotating speed machinery of 700r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, then add 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after reaction 12h; The 4-butyl ammonium hydrogen sulfate that adds again 0.6 part, the toluhydroquinone of 0.3 part, 10 parts of glycidyl acrylates, are warming up to 105 ℃ 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 solution of 10 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N3;
(2) at gained, can in the acrylic ester prepolymer N3 of UV photocuring, add 4 parts of 2-hydroxyl-2 methyl isophthalic acid-phenyl-1-acetone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 4:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts, vinylformic acid, 60 parts of ethoxy ethoxy ethyl propylene acid esters, 20 parts of butyl acrylates, 2.5 parts of azo dicyclohexyl formonitrile HCNs, in the environment of logical nitrogen, with the rotating speed machinery of 600r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, then add 1 part of azo dicyclohexyl formonitrile HCN, continue after reaction 13h; The benzyl triethyl ammonium bromide that adds again 0.8 part, the MEHQ of 0.4 part, 16 parts of glycidyl acrylates, are warming up to 105 ℃ 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 solution of 8 parts and above-mentioned reaction system, obtain acrylic ester prepolymer N4;
(2) at gained, can in the acrylic ester prepolymer N4 of UV photocuring, add 3 parts of isopropyl phenyl-2-hydroxy-2-methyl acetone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 5:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 40 parts of methacrylic acids, 50 parts of ethoxy ethoxy ethyl propylene acid esters, 10 parts of methyl methacrylates, 2 parts of Diisopropyl azodicarboxylates, in the environment of logical nitrogen, with the rotating speed machinery of 800r/min, be stirred to and mix, be warming up to 75 ℃, reaction 0.5h, then add 1 part of Diisopropyl azodicarboxylate, continue after reaction 10h; The bromination tributyl benzylamine that adds again 0.5 part, the 2-Tert. Butyl Hydroquinone of 0.2 part, 12 parts of glycidyl methacrylate, are warming up to 106 ℃ 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 solution of 6 parts and above-mentioned reaction system, obtain methacrylate prepolymers N5;
(2) at gained, can in the methacrylate prepolymers N5 of UV photocuring, add 1 part of 1-hydroxyl-phenylcyclohexyl ketone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 400nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 6:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 10 parts of methacrylic acids, 80 parts of ethoxy ethoxy ethyl propylene acid esters, 10 parts of β-dimethyl-aminoethylmethacrylates, 3 parts of initiators, in the environment of logical nitrogen, with the rotating speed machinery of 900r/min, be stirred to and mix, be warming up to 80 ℃, reaction 0.5h, then add 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after reaction 15h; The trioctylphosphine brometo de amonio that adds 1 part, the 2,5 di tert butyl hydroquinone of 0.5 part, 6 parts of glycidyl methacrylate, are warming up to 108 ℃ 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 solution of 10 parts and above-mentioned reaction system, obtain methacrylate prepolymers N6;
(2) at gained, can in the methacrylate prepolymers N6 of UV photocuring, add 5 parts of 2-methyl isophthalic acids-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 200nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 7:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts of methacrylic acids, 50 parts of ethoxy ethoxy ethyl propylene acid esters, 30 parts of butyl methacrylate, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), in the environment of logical nitrogen, with the rotating speed machinery of 500r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, then add 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after reaction 12h; The 4-butyl ammonium fluoroborate that adds again 0.6 part, the Resorcinol of 0.3 part, 15 parts of glycidyl methacrylate, are warming up to 103 ℃ 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 solution of 7 parts and above-mentioned reaction system, obtain methacrylate prepolymers N7;
(2) at gained, can in the methacrylate prepolymers N7 of UV photocuring, add 4 parts of 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 preparation of UV-curable water-borne acrylic ester polymer coating for embodiment 8:BOPP
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts of methacrylic acids, 60 parts of ethoxy ethoxy ethyl propylene acid esters, 20 parts of N-Hexyl methacrylates, 2.5 parts of azo dicyclohexyl formonitrile HCNs, in the environment of logical nitrogen, with the rotating speed machinery of 600r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, then add 1 part of azo dicyclohexyl formonitrile HCN, continue after reaction 13h; The tri-n-octyl methyl ammonium chloride that adds again 0.8 part, the 2-Tert. Butyl Hydroquinone of 0.4 part, 16 parts of glycidyl methacrylate, are warming up to 104 ℃ 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 solution of 8 parts and above-mentioned reaction system, obtain methacrylate prepolymers N8;
(2) at gained, can in the methacrylate prepolymers N8 of UV photocuring, add 3 part 2,4,6-Three methyl Benzene formyl diethyl phosphonate, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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: do not contain the preparation of the acrylic ester polymer coating of optical active group
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts of methacrylic acids, 50 parts of ethoxy ethoxy ethyl propylene acid esters, 30 parts of butyl methacrylate, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), in the environment of logical nitrogen, with the rotating speed machinery of 500r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, then add 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after 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 solution of 7 parts and above-mentioned reaction system, obtain not the acrylic ester prepolymer N9 containing optical active group;
(2) the acrylic ester prepolymer N9 that does not contain optical active group of gained is coated with to the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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: do not contain the preparation of the acrylic ester polymer of oxyethyl group side chain
(1) by weight, in the reactor with agitator, prolong, add successively 20 parts of methacrylic acids, 50 parts of N-Hexyl methacrylates, 30 parts of butyl methacrylate, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), in the environment of logical nitrogen, with the rotating speed machinery of 500r/min, be stirred to and mix, be warming up to 78 ℃, reaction 0.5h, add again 1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), continue after reaction 12h, the 4-butyl ammonium fluoroborate that adds 0.6 part, the Resorcinol of 0.3 part, 15 parts of glycidyl methacrylate, are warming up to 103 ℃ 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 solution of 7 parts and above-mentioned reaction system, make not the acrylic ester prepolymer N10 containing oxyethyl group side chain;
(2) gained containing not adding 3 parts of benzophenone in the acrylic ester prepolymer T2 of oxyethyl group side chain, mix, and be coated with the thick film of 0.08mm at BOPP film surface, be placed in stink cupboard 1 hour, the ultraviolet lamp 4cm place that it is 365nm that moisture is placed on apart from wavelength after volatilizing completely, irradiate after 5 seconds performance as follows:
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 that adopts 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 while not existing ultraviolet curing group polymer-coated to test on BOPP film surface, because force of cohesion is not enough, the adhesive property index recording is lower than the index of photo curable polymkeric substance in embodiment; The performance test results from comparative example 2, while using acrylic ester polymer containing oxyethyl group side chain to be coated in BOPP film surface to test, because mobility is not good enough, segment is easily frozen in solidification process, adhesive property is not good enough, and the volumetric shrinkage of acrylic ester polymer coating is larger, the volumetric shrinkage that contains the acrylic ester polymer coating of oxyethyl group side chain in embodiment drops to below 2%, and shearing resistance is improved with performances such as holding the sticky time.
As can be seen here, UV-curable water-borne acrylic ester polymer coating for the BOPP the present invention relates to, owing to introducing oxyethyl group in acrylic ester prepolymer side chain, can make acrylic ester prepolymer there is lower shrinking percentage, good snappiness and mobility, be conducive to prepolymer sprawling on BOPP film surface; Appropriate water-based group in structure, the water-borne coatings of the environmental protection can be made into; In the side chain of acrylic ester prepolymer, introduce the reactive group can carry out ultraviolet light polymerization, can be in the situation that not adding small molecules auxiliary agent the effective force of cohesion of raising system, increase the service life, energy-conserving and environment-protective.The polypropylene structure of the backbone of acrylate and BOPP has similarity, and the acrylic ester polymer and the BOPP film that as coating, use have good sticking power.Use this acrylic ester prepolymer as the main component of binding agent, can be effectively by together with the material binding of BOPP film and opposed polarity, be conducive to BOPP film in the application in the fields such as printing, bag, thereby reach the effect that the technology of the present invention improves.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
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.
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 methyl phenyl ketone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl phenyl-2-hydroxy-2-methyl acetone, 1-hydroxyl-phenylcyclohexyl ketone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, 2-phenyl-2, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2, 4, at least one in 6-Three methyl Benzene formyl diethyl phosphonate and benzophenone.
4. according to a preparation method for the UV-curable water-borne acrylic ester polymer coating described in claim 1～3 any one, it is characterized in that comprising the following steps:
(methyl) vinylformic acid, ethoxy ethoxy ethyl propylene acid esters, (methyl) alkyl acrylate, part initiator are mixed, reacting by heating, then add residue initiator to continue 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 UV-curable water-borne acrylic ester polymer coating for BOPP.
5. the preparation method of UV-curable water-borne acrylic ester polymer coating according to claim 4, 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, vinylformic acid isopentyl ester and (methyl) Ethyl acrylate.
6. the preparation method of UV-curable water-borne acrylic ester polymer coating according to claim 4, 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.
7. the preparation method of UV-curable water-borne acrylic ester polymer coating according to claim 4, is characterized in that: the mass ratio of (methyl) used vinylformic acid, ethoxy ethoxy ethyl propylene acid esters, (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.
8. the preparation method of UV-curable water-borne acrylic ester polymer coating according to claim 4, is characterized in that: described reacting by heating refers to 500～1000r/min stirring reaction 0.5h at 75～80 ℃; Described reacting by heating is carried out in the environment of logical nitrogen; Described continuation reaction refers to react 10～15h; Described temperature reaction refers at 102～110 ℃ of reaction 4～5h; The mass ratio of basic solution used and acrylic ester prepolymer M is (5～10): 100.
9. the preparation method of UV-curable water-borne acrylic ester polymer coating according to claim 4, is characterized in that: described basic solution is by being dissolved in 2～5 weight part alkaline reagentss in 10 weight parts waters and preparing; Described alkaline reagents refers at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide and ammoniacal liquor.
10. the application as binding agent according to the UV-curable water-borne acrylic ester polymer coating described in claim 1～3 any one, is characterized in that being realized by following methods:
BOPP is coated in to BOPP with UV-curable water-borne acrylic ester polymer coating upper, air-dry after, be placed in to locate to irradiate under ultraviolet lamp and solidify; The wavelength region of described ultraviolet lamp is 200～400nm.
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